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1 Organocatalytic Enantioselective Desymmetrization of Cyclic Enones via Phosphine Promoted [3+2] Annulations Nathalie Pinto, Pascal Retailleau, Arnaud Voituriez and Angela Marinetti* Institut de Chimie des Substances Naturelles CNRS UPR 2301, Centre de Recherche de Gif 1 av. de la Terrasse, 91198 Gif sur Yvette, France [email protected] Table of Contents : 1) General methods 2) Substrates 3) Phosphine promoted [3+2] cyclisations on enones 1. 4) NMRspectra and HPLC analysis Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010

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  • 1

    Organocatalytic Enantioselective Desymmetrization of Cyclic

    Enones via Phosphine Promoted [3+2] Annulations

    Nathalie Pinto, Pascal Retailleau, Arnaud Voituriez and Angela Marinetti*

    Institut de Chimie des Substances Naturelles

    CNRS UPR 2301, Centre de Recherche de Gif

    1 av. de la Terrasse, 91198 Gif sur Yvette, France

    [email protected]

    Table of Contents :

    1) General methods

    2) Substrates

    3) Phosphine promoted [3+2] cyclisations on enones 1.

    4) NMRspectra and HPLC analysis

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 2

    1) General methods

    All reactions were run under argon by using standard techniques for manipulating air-

    sensitive compounds. Anhydrous solvents were obtained by filtration through drying columns

    (THF, Et2O, CH2Cl2). All reagents were of commercial quality and were used without further

    purification. Flash column chromatography was performed using 40-63 mesh silica. Nuclear

    magnetic resonance spectra (1H, 13C, 31P) were recorded either on Brucker AV 500 or AV 300

    spectrometers. IR spectra were recorded with a Perkin-Elmer FT-IR spectrophotometer. High

    resolution mass spectra (HRMS-ESI) were obtained on LCT Waters equipment. Optical

    rotations were determined with a JASCO P-1010 polarimeter. HPLC was performed at a

    column temperature of 30C on a Waters 2695 Separations Module equipped with a diode

    array UV detector. Data are reported as follows: column type, eluent, flow rate, retention

    time.

    2) Substrates

    4-methylcyclohexanone, 4-tert-butylcyclohexanone, 4-phenylcyclohexanone and 4-

    isopropylcyclohexanone are commercially available. The diarylidenecyclohexanones

    1a,c,d,f,e are known compounds. 1 , 2 They have been prepared as shown hereafter. 2,4-

    dibenzylidenebicyclo[3.1.0]hexan-3-one 4a and 2,4-dibenzylidene-6-

    methylbicyclo[3.1.0]hexan-3-one 4b were prepared according to literature procedure.3

    (2E,6E)-2,6-dibenzylidene-4-methylcyclohexanone 1a. Method

    A: 4-methylcyclohexanone (10 mmol, 1.12 g) was dissolved in

    a mixture of ethanol (20 mL) and water (10 mL).

    Benzaldehyde (20 mmol, 2 mL) and NaOH [1M] (10 mL) were

    then added at 0C. The mixture was stirred at room temperature overnight. The yellow

    precipitate was filtrated and the desired compound was obtained as a yellow solid (2.27 g,

    79%). 1H NMR (500 MHz, CDCl3) 7.81 (bs, 2H, C=CHC6H5), 7.50-7.25 (m, 10H), 3.07

    1 Frey, H. Synthesis 1992, 387-390. 2 Dimmock, J. R.; Padmanilayam, M. P.; Zello, G. A.; Nienaber, K. H.; Allen, T. M.; Santos, C. L.; De Clercq, E.; Balzarini, J.; Manavathu E. K. ; Stables, J. P. Eur. J. Med. Chem., 2003, 38, 169-177 3 Kearley, M. L.; Lahti, P. M. Tetrahedron Lett.1991, 32, 5869-5872 ; Kearley, M. L.; Ichimura, A. S.; Lahti, P. M. J. Am. Chem. Soc. 1995, 117, 5235-5244; Flaugh, M. E.; Crowell, T. A.; Farlow, D. S. J. Org. Chem. 1980, 45, 5399-5400.

    O

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 3

    (dd, 2JAB = 16.0, 3J = 3.5 Hz, 2H, CHH), 2.52 (m, 2H, 2CHH), 1.89 (m, 1H, CHCH3), 1.08 (d, 3J = 6.5 Hz, 3H, CHCH3); 13C NMR (75 MHz, CDCl3) 190.3 (Cq), 137.3 (C=CHC6H5),

    136.1 (Cq), 135.5 (Cq), 130.5 (CH), 128.7 (CH), 128.5 (CH), 36.6 (CH2), 29.6 (CHCH3), 21.8

    (CHCH3); IR: max= 2957, 1660, 1603, 1568, 1444, 1288, 1240, 1142, 931, 770, 755, 692 cm-

    1; MS (ESI) m/z : 289 [M+H]+; Melting point: 96-97C.

    (2E,6E)-2,6-dibenzylidene-4-isopropylcyclohexanone 1b.

    Method A was employed, starting from 4-isopropyl-

    cyclohexanone (1.6 mmol, 0.25 mL) and benzaldehyde (3.2

    mmol, 0.35 mL). The product was obtained as a yellow solid

    (330 mg, 65%). 1H NMR (500 MHz, CDCl3) 7.8 (br, 2H), 7.50-7.30 (m, 10H), 3.06 (dd, J =

    15.5, 3.0 Hz, 2H, CH2), 2.60-2.55 (m, 2H, CH2), 1.64 (m, J = 6.5 Hz, 1H, CH), 1.60-1.50 (m,

    1H, CH), 0.91 (d, 3J = 7.0 Hz, 6H, CH3); 13C NMR (75 MHz, CDCl3) 190.7 (Cq), 137.3

    (C6H5CH=C), 136.2 (Cq), 135.8 (Cq), 130.5 (CH), 128.7 (CH), 128.6 (CH), 40.4 (CH), 31.7

    (CH), 31.6 (CH2), 19.9 (CH3); IR: max= 1661, 1570, 1444, 1291, 1154, 775, 693 cm-1; MS

    (ESI) m/z : 339 [M+Na]+; Melting point: 102-103C.

    (2E,6E)-2,6-dibenzylidene-4-tert-butylcyclohexanone 1c. Method

    A: 4-tert-butylcyclohexanone (10 mmol, 1.54 g), was dissolved

    in a mixture of ethanol (20 mL) and water (10 mL).

    Benzaldehyde (20 mmol, 2 mL) and NaOH [1M] (10 mL) were

    then added and the resulting mixture was heated at 50C and stirred overnight. The yellow

    precipitate was filtrated and the desired compound was obtained as a yellow solid after

    crystallization in ethanol (1.79 g, 54%). 1H NMR (500 MHz, CDCl3) 7.80-7.75 (m, 2H),

    7.50-7.30 (m, 10H), 3.17 (dd, J = 15.5, 2.0 Hz, 2H, CH2), 2.50-2.40 (m, 2H, CH2), 1.49 (m,

    1H, CH), 0.95 (s, 9H, CH3); 13C NMR (75 MHz, CDCl3) 190.8 (Cq), 137.0 (CH), 136.3

    (Cq), 136.2 (Cq), 130.4 (CH), 128.7 (CH), 128.6 (CH), 44.5 (CH), 32.7 (Cq), 29.7 (CH2),

    27.4 (CH3); IR: max= 2959, 1660, 1603, 1445, 1244, 1157, 983, 776, 693 cm-1; MS

    (ESI) m/z : 353 [M+Na]+; Melting point: 137-138C.

    (2E,6E)-2,6-dibenzylidene-4-phenylcyclohexanone 1d.

    Method A was employed starting from 4-phenylcyclohexanone

    (2.87 mmol, 500 mg) and benzaldehyde (5.74 mmol, 0.9 mL).

    The product was obtained as a yellow solid from the crude

    O

    O

    O

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 4

    reaction mixture by filtration (958 mg, 96%). 1H NMR (500 MHz, CDCl3) 7.90-7.85 (m,

    2H), 7.45-7.25 (m, 15H), 3.35-3.30 (m, 2H), 3.10-3.00 (m, 3H); 13C NMR (75 MHz, CDCl3)

    189.7 (Cq), 144.8 (Cq), 138.0 (CH), 135.9 (Cq), 135.2 (Cq), 130.6 (CH), 128.89 (CH),

    128.87 (CH), 128.6 (CH), 126.99 (CH), 126.97 (CH), 41.0 (CH), 36.1 (CH2); IR: max= 1733,

    1660, 1598, 1443, 1288, 1146, 983, 750 691 cm-1; MS (ESI) m/z : 373 [M+Na]+;Melting

    point: 134-135C.

    (2E,6E)-4-tert-butyl-2,6-bis(4-methoxybenzylidene)

    cyclohexanone 1e. Method A was employed starting

    from 4-tert-butylcyclohexanone (10 mmol, 1.54 g)

    and 4-methoxybenzaldehyde (20 mmol, 2.4 mL).

    The product was obtained as a yellow solid (2.42 g,

    62%). 1H NMR (500 MHz, CDCl3) 7.73 (m, 2H), 7.45 (d, J = 8.5 Hz, 4H), 6.95 (d, J = 8.5

    Hz, 4H), 3.85 (s, 6H, OMe), 3.15 (dd, J = 15.5, 2.5 Hz, 2H, CH2), 2.44 (t, J ~ 14 Hz, 2H),

    1.48 (tt, J = 13.0, 3.0 Hz, 1H), 0.97 (s, 9H); 13C NMR (75 MHz, CDCl3) 190.5 (Cq), 160.0

    (2Cq), 136.5 (CH), 134.4 (Cq), 132.3 (CH), 128.9 (Cq), 114.1 (CH), 55.4 (OCH3), 44.5 (Cq),

    32.6 (Cq), 29.7 (CH2), 27.5 (CH3); IR: max= 2951, 1664, 1507, 1291, 1254, 1169, 1029, 830,

    770 cm-1; MS (ESI) m/z : 413 [M+Na]+; Melting point: 171-172C.

    (2E,6E)-4-tert-butyl-2,6-bis(4-methylbenzylidene)cyclo-

    hexanone 1f. Method A was employed with 4-tert-

    butylcyclohexanone (10 mmol, 1.54 g) and 4-

    methylbenzaldehyde (20 mmol, 2.35 mL)). The product

    was obtained as a yellow solid (3.10 g, 87%). 1H NMR (500 MHz, CDCl3) 7.78 (m, 2H),

    7.41 (d, J = 7.5 Hz, 4H), 7.25 (d, J = 7.5 Hz, 4H), 3.19 (d, J = 15.0 Hz, 2H), 2.46 (t, J ~ 14

    Hz, 2H), 2.41 (s, 6H), 1.51 (t, J = 12.5 Hz, 1H), 0.99 (s, 9H); 13C NMR (75 MHz, CDCl3)

    190.7 (Cq), 138.9 (Cq), 136.9 (CH), 135.6 (Cq), 133.4 (Cq), 130.5 (CH), 129.3 (CH), 44.5

    (CH), 32.7 (Cq), 29.7 (CH2), 27.4 (C(CH3)3), 21.5 (CH3); IR: max= 2961, 2358, 1663, 1573,

    1315, 1174, 930, 817, 666 cm-1; MS (ESI) m/z : 381 [M+Na]+; Melting point: 156-157C.

    (2E,6E)-4-tert-butyl-2,6-bis(4-chlorobenzylidene)cyclo-

    hexanone 1g. Method A was employed starting from 4-

    tert-butylcyclohexanone (10 mmol, 1.54 g) and 4-

    chlorobenzaldehyde (20 mmol, 2.8 g). The product was

    obtained as a yellow solid (3.25 g, 82%). 1H NMR (500 MHz, CDCl3) 7.65 (bs, 2H), 7.39

    O

    O

    MeO OMe

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 5

    (bs, 8H), 3.09 (m, 2H), 2.41 (m, 2H), 1.47 (m, 1H), 0.94 (s, 9H); 13C NMR (75 MHz, CDCl3)

    190.2 (Cq), 136.6 (Cq), 135.8 (CH), 134.7 (Cq), 134.5 (Cq), 131.6 (CH), 128.9 (CH), 44.5

    (CH), 32.7 (Cq), 29.6 (CH2), 27.4 (CH3); IR: max= 2958, 1663, 1577, 1558, 1404, 1241,

    1092, 983, 928, 823, 704 cm-1; MS (ESI) m/z : 421 [M+Na]+; Melting point: 177-178C.

    (2E,6E)-4-tert-butyl-2,6-bis(naphthalen-1-ylmethylene)-

    cyclohexanone 1h. Method A was employed starting from 4-

    tert-butylcyclohexanone (10 mmol, 1.54 g) and 1-

    naphthaldehyde (20 mmol, 2.7 mL). The product was

    obtained as a yellow solid (1.98 g, 46%). 1H NMR (300

    MHz, CDCl3) 8.43 (m, 2H), 8.10-8.05 (m, 2H), 7.95-7.85 (m, 4H), 7.60-7.45 (m, 8H), 3.06

    (dd, J = 15.0, 2.4 Hz, 2H), 2.38 (m, 2H), 1.53 (tt, J = 12.6, 3.3 Hz, 1H), 0.78 (s, 9H); 13C

    NMR (75 MHz, CDCl3) 190.5 (Cq), 138.3 (Cq), 135.4 (CH), 133.7 (Cq), 133.3 (Cq), 132.2

    (Cq), 129.0 (CH), 128.7 (CH), 126.9 (CH), 126.6 (CH), 126.3 (CH), 125.2 (CH), 124.9 (CH),

    45.1 (CH), 32.7 (Cq), 29.9 (CH2), 27.2 (CH3); IR: max= 2955, 1593, 1231, 1196, 1156, 968,

    861, 778 cm-1; MS (ESI) m/z : 453 [M+Na]+; Melting point: 146-148C.

    (2E,6E)-4-tert-butyl-2,6-bis(naphthalen-2-

    ylmethylene)cyclohexanone 1i. Method A was

    employed with 4-tert-butylcyclohexanone (5 mmol,

    770 mg) and 2-naphthaldehyde (10 mmol, 1.56 g).

    The product was obtained as a yellow solid (1.79 g,

    83%). 1H NMR (500 MHz, CDCl3) 7.96 (bs, 4H), 7.90-7.80 (m, 6H), 7.60 (d, J = 8.5 Hz,

    2H), 7.55-7.45 (m, 4H), 3.31 (d, J = 15.5 Hz, 2H), 2.58 (t, J ~14 Hz, 2H), 1.55-1.50 (m, 1H),

    0.97 (s, 9H); 13C NMR (75 MHz, CDCl3) 190.7 (Cq), 137.1 (CH), 136.6 (Cq), 133.8 (2Cq),

    133.3 (Cq), 133.2 (Cq), 130.4 (CH), 128.6 (CH), 128.2 (CH), 127.8 (CH), 127.7 (CH), 127.0

    (CH), 126.6 (CH), 44.7 (CH), 32.7 (Cq), 29.8 (CH2), 27.4 (CH3): IR: max= 2356, 1692, 1595,

    1563, 1429, 1297, 992, 747, 724 cm-1; MS (ESI) m/z : 453 [M+Na]+; Melting point: 191-

    193C.

    (2E,6E)-4-tert-butyl-2,6-bis(furan-2-ylmethylene)cyclohexanone

    1j. Method A was employed starting from 4-tert-

    butylcyclohexanone (10 mmol, 1.54 g) and 2-furaldehyde (20

    mmol, 1.65 mL). The product (2.45g, 79%) was obtained as a

    yellow solid. 1H NMR (300 MHz, CDCl3) 7.58 (d, J = 1.8 Hz, 2H), 7.53 (d, J = 2.4 Hz,

    OO

    O

    O

    O

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 6

    2H), 6.67 (d, J = 3.4 Hz, 2H), 6.53 (dd, J = 3.4, 1.8 Hz, 2H), 3.38 (dd, J = 16.5, 3.0 Hz, 2H),

    2.41 (m, 2H), 1.65-1.55 (tt, J = 12.9, 3.6 Hz, 1H), 1.06 (s, 9H); 13C NMR (75 MHz, CDCl3)

    189.5 (Cq), 152.9 (Cq), 144.7 (CH), 133.3 (Cq), 123.4 (CH), 116.2 (CH), 112.4 (CH), 43.3

    (CH), 32.2 (Cq), 29.4 (CH2), 27.5 (CH3); IR: max= 2959, 1596, 1477, 1307, 1239, 730 cm-1;

    MS (ESI) m/z : 333 [M+Na]+; Melting point: 136-138C.

    3) Phosphine promoted [3+2] cyclisations on enones 1.

    Procedure a: Ethyl 2,3 butadienoate (0,40 mmol) was added to a mixture of enones 1 (0.20

    mmol) and cyclohexyldiphenyl phosphine (10 mol %, 0.020 mmol, 5.4 mg) in degazed

    toluene (0.7 mL) under argon atmosphere. The solution was stirred at 40C until completion.

    The crude mixture was concentrated in vacuo. Diastereomeric ratios were measured by NMR

    on the crude mixture, based on integration of the C=CHPh signals at about 7.5 ppm. The final

    product was purified by flash chromatography on silica gel (5% EtOAc / heptanes).

    Procedure b: Ethyl 2,3 butadienoate (0,30 mmol) was added to a mixture of enones 1 (0.15

    mmol) and either FerroPHANE, A, or t-Bu-Binepine, B (10 mol %, 0.015 mmol) in degazed

    toluene (0.5 mL) under argon atmosphere. The solution was stirred at 80C until completion.

    The crude mixture was concentrated in vacuo. Diastereomeric ratios were measured by NMR

    on the crude mixture, based on integration of the C=CHPh signals at about 7.5 ppm. The final

    product was purified by flash chromatography on silica gel (5% EtOAc / heptanes).

    (E)-ethyl 7-benzylidene-9-methyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-

    carboxylate 2a. Procedure a (catalyst CyPPh2): 95% yield, 90/10 dr;

    Procedure b (catalyst (S,S)-FerroPHANE): 91% yield, 76% ee, 80/20 dr;

    Pale yellow oil; 1H NMR (300 MHz, CDCl3) 7.57 (bs, 1H,

    C6H5CH=C), 7.35-7.10 (m, 10H), 6.91 (m, 1H, CH2CH=C), 4.15-4.00

    (m, 3H, CH2CH3, CH2CHC6H5), 2.88 (ddd, 2JAB = 18.0 Hz, 3J = 10,2, 1.8 Hz, 1H,

    CH2CH=C), 2.75-2.65 (m, 2H, CH2CH=C, CH2CHCH3), 2.13 (ddd, 2JAB = 15.3 Hz, 3J = 12.6,

    3.0 Hz, 1H, CH2CHCH3), 1.85 (dt, 2JAB = 13.8, 3J 4J = 3.0 Hz, 1H, CH2CHCH3), 1.60 (t, 2J

    3J = 13 Hz, 1H, CH2CHCH3), 1.18 (t, 3J = 6.9 Hz, 3H, CH2CH3), 0.54 (d, 3J = 6.6 Hz, 3H,

    CHCH3), 0.40-0.25 (m, 1H, CHCH3); 13C NMR (75 MHz, CDCl3) 205.2 (Cq), 163.8 (Cq),

    143.4 (Cq), 143.3 (CH2CH=C), 139.1 (Cq), 136.7 (Cq), 136.1 (Cq), 136.0 (C6H5CH=C),

    130.5 (2CH), 128.6 (2CH), 128.5 (CH), 128.4 (2CH), 128.4 (2CH), 127.5 (CH), 62.9 (Cq),

    60.7 (CH2CH3), 56.1 (CH2CHC6H5), 37.5 (CH2), 36.6 (CH2), 35.7 (CH2), 26.5 (CHCH3), 22.0

    (CHCH3), 14.3 (CH2CH3); IR: max= 2924, 1706, 1592, 1491, 1445, 1242, 1075, 1026, 904,

    O

    Ph

    Ph

    EtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 7

    750, 696 cm-1; HRMS (ESI) calcd. For C27H28NaO3 [M+Na]+: 423.1936, found: 423.1921;

    HPLC Analysis: 76% ee [Daicel CHIRACEL IC, 10% iPrOH/n-heptane, 1mL/min, 300 nm,

    retention times: 19.8 min (major) and 34.8 min (minor)]. Minor diastereoisomer: selected 1H

    NMR data (300 MHz, CDCl3) 7.67 (bs), 6.99 (dd, J = 3.0, 2.0 Hz), 4.21 (dd, J = 11.1, 7.5

    Hz), 1.40 (t, J = 13.0 Hz), 0.75 (d, J = 6.6 Hz).

    (E)-ethyl 7-benzylidene-9-isopropyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-

    1-carboxylate 2b. Procedure a (catalyst CyPPh2): 93% yield, 85/15 dr;

    Procedure b (catalyst (S,S)-FerroPHANE): 44% yield, 82% ee, 80/20 dr;

    Pale yellow oil; 1H NMR (500 MHz, CDCl3) 7.65 (d, J = 2.5 Hz, 1H),

    7.40-7.15 (m, 10H), 7.00 (t, J = 2.0 Hz, 1H), 4.25-4.10 (m, 3H), 2.96

    (ddd, J = 18.0, 10.0, 2.0 Hz, 1H), 2.80-2.75 (m, 2H), 2.24 (ddd, J = 15.5, 12.2, 3.0 Hz, 1H),

    1.93 (dt, J = 13.5, 3.0 Hz, 1H), 1.69 (t, J = 13.0 Hz, 1H), 1.25 (t, J = 7.0 Hz, 3H), 1.20-1.10

    (m, 1H), 0.57 (d, J = 6.5 Hz, 3H), 0.54 (d, J = 6.5 Hz, 3H), 0.30-0.20 (m, 1H); 13C NMR (75

    MHz, CDCl3) 205.4 (Cq), 163.8 (Cq), 143.5 (CH), 143.3 (Cq), 139.1 (Cq), 136.9 (Cq),

    136.2 (Cq), 136.1 (CH), 130.4 (2CH), 128.9 (2CH), 128.5 (2CH), 128.4 (3CH), 127.4 (CH),

    62.8 (Cq), 60.6 (CH2), 55.9 (CH), 36.6 (CH), 35.8 (CH2), 32.3 (CH), 31.8 (CH2), 31.7 (CH2),

    19.6 (CH3), 18.9 (CH3), 14.2 (CH3); IR: max= 2956, 2360, 1708, 1592, 1446, 1326, 1244,

    1091, 1027, 911, 865 cm-1; HRMS (ESI) calcd. For C29H32NaO3 [M+Na]+: 451.2249, found:

    451.2259; HPLC Analysis: 82% ee [Daicel CHIRACEL IA, 10% iPrOH/n-heptane,

    1mL/min, 300 nm, retention times: 7.7 min (minor) and 10.2 min (major)]; Minor

    diastereoisomer: selected 1H NMR data (500 MHz, CDCl3) 7.68 (br), 7.04 (dd, J = 2.9, 1.95

    Hz), 0.73 (dd, J = 7.0, 5.5 Hz).

    (E)-ethyl 7-benzylidene-9-tert-butyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-

    1-carboxylate 2c. Procedure a (catalyst CyPPh2): 92% yield, >95/5 dr;

    Procedure b (catalyst (S,S)-FerroPHANE): 98% yield, 92% ee, >95/5 dr;

    White solid; 1H NMR (300 MHz, CDCl3) 7.56 (d, J = 2.4 Hz, 1H), 7.30-

    7.10 (m, 10H), 6.95 (t, J = 2.7 Hz, 1H), 4.15-4.00 (m, 3H), 2.90 (ddd, J =

    18.3, 9.6, 2.1 Hz, 1H), 2.83 (dt, J = 14.4, 3.0 Hz, 1H), 2.71 (ddd, J = 18.3, 8.1, 3.0 Hz, 1H),

    2.15 (td, J = 15.0, 2.7 Hz, 1H), 1.92 (dt, J = 13.8, 2.7 Hz, 1H), 1.65 (t, J = 13.2 Hz, 1H), 1.18

    (t, J = 6.9 Hz, 3H), 0.49 (s, 9H), 0.27 (tt, J = 13.0, 3.5 Hz, 1H); 13C NMR (75 MHz, CDCl3)

    205.4 (Cq), 163.8 (Cq), 143.6 (CH), 143.3 (Cq), 139.0 (Cq), 137.4 (Cq), 136.2 (Cq), 135.9

    (CH), 130.2 (2CH), 129.1 (2CH), 128.5 (2CH), 128.4 (2CH), 128.3 (CH), 127.4 (CH), 63.0

    (Cq), 60.6 (CH2), 55.8 (CH), 40.2 (CH), 35.8 (CH2), 32.2 (Cq), 29.9 (CH2), 29.2 (CH2), 27.0

    O

    Ph

    Ph

    EtOOC

    O

    PhPh

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 8

    (3CH3), 14.2 (CH3); IR: max= 2946, 1697, 1667, 1588, 1370, 1327, 1243, 1232, 1162, 1095,

    1027, 754, 697 cm-1; HRMS (ESI) calcd. For C30H34NaO3 [M+Na]+: 465.2406, found:

    465.2397; HPLC Analysis: 92% ee [Daicel CHIRACEL IC, 10% iPrOH/n-heptane,

    1mL/min, 300 nm, retention times: 16.4 min (major) and 40.0 min (minor)]; []D24 = + 290 (c

    = 0.91, CHCl3); Melting point: 128-130C.

    (E)-ethyl 7-benzylidene-6-oxo-1,9-diphenylspiro[4.5]dec-1-ene-2-

    carboxylate 2d. Procedure a (catalyst CyPPh2): 86% yield, 90/10 dr;

    Procedure b (catalyst (S,S)-FerroPHANE): 98% yield, 92% ee, 85/15

    dr; White solid; 1H NMR (500 MHz, CDCl3) 7.79 (bs, 1H), 7.40-7.15

    (m, 13H), 7.02 (bs, 1H), 6.80 (d, J = 7.5 Hz, 2H), 4.30-4.20 (m, 3H),

    3.05-2.90 (m, 2H), 2.85-2.75 (m, 2H), 2.24 (dd, J = 14.0, 13.0 Hz, 1H), 2.18 (d, J = 13.0 Hz,

    1H), 1.65-1.60 (m, 1H), 1.33 (t, J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) 204.7 (Cq),

    163.8 (Cq), 145.1 (Cq), 143.4 (Cq), 143.1 (CH), 138.9 (Cq), 136.9 (CH), 136.4 (Cq), 135.8

    (Cq), 130.5 (2CH), 128.9 (2CH), 128.8 (2CH), 128.6 (2CH), 128.5 (3CH), 127.7 (CH), 126.8

    (2CH), 126.5 (CH), 63.3 (Cq), 60.8 (CH2), 56.2 (CH), 37.8 (CH), 37.2 (CH2), 35.5 (CH2),

    35.2 (CH2), 14.3 (CH3); IR: max= 2932, 1697, 1592, 1371, 1327, 1240, 1151, 760, 747, 693

    cm-1; HRMS (ESI) calcd. For C32H30NaO3 [M+Na]+: 485.2093, found: 485.2073; HPLC

    Analysis: 92% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane, 1ml/min, 270 nm, retention

    times: 13.8 min (minor) and 18.4 min (major)]; Melting point: 165-166C.

    (E)-tert-butyl 7-benzylidene-9-methyl-6-oxo-4-phenylspiro[4.5]dec-

    1-ene-1-carboxylate 3a. Procedure a (catalyst CyPPh2): 90% yield,

    85/15 dr; Procedure b (catalyst (S,S)-FerroPHANE): 86% yield,

    90% ee, 80/20 dr; White solid; 1H NMR (300 MHz, CDCl3) 7.57

    (d, J = 2.4 Hz, 1H), 7.35-7.05 (m, 10H), 6.85 (t, J = 2.4 Hz, 1H),

    3.98 (m, 1H), 2.86 (ddd, J = 17.7, 10.2, 2.1 Hz, 1H), 2.70-2.60 (m,

    1H), 2.08 (ddd, J = 15.3, 12.6, 3.0 Hz, 1H), 1.83 (dt, J = 13.8, 3.0 Hz, 1H), 1.59 (t, J = 12.6

    Hz, 2H), 1.37 (s, 9 H), 0.54 (d, J = 6.6 Hz, 3H), 0.35-0.25 (m, 1H); 13C NMR (75 MHz,

    CDCl3) 205.1 (Cq), 163.1 (Cq), 144.6 (Cq), 142.8 (CH), 139.3 (Cq), 136.8 (Cq), 136.2 (Cq),

    135.9 (CH), 130.4 (2CH), 128.6 (2CH), 128.44 (CH), 128.41 (4CH), 127.43 (CH), 81.2 (Cq),

    62.9 (Cq), 56.5 (CH), 37.5 (CH2), 36.7 (CH2), 35.4 (CH2), 28.2 (CH3), 26.3 (CH), 22.0 (CH3);

    IR: max= 2919, 1693, 1671, 1590, 1445, 1332, 1244, 1148, 1076, 1022, 847 cm-1; Melting

    point: 142-144C; HRMS (ESI) calcd. For C29H32NaO3 [M+Na]+: 451.2249, found:

    OCOOtBu

    Ph

    O

    PhPh

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 9

    451.2256; HPLC Analysis: 90% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane,

    1mL/min, 300 nm, retention times: 7.4 min (minor) and 12.1 min (major)].

    (E)-tert-butyl 7-benzylidene-9-isopropyl-6-oxo-4-phenylspiro[4.5]-

    dec-1-ene-1-carboxylate 3b. Procedure a (catalyst CyPPh2): 91%

    yield, 70/30 dr; Procedure b (catalyst (S,S)-FerroPHANE): 43%

    yield, 86% ee, 70/30 dr; Pale yellow oil; Selected data from the

    mixture of two diastereoisomers: 1H NMR (300 MHz, CDCl3)

    7.67 (d, J = 2.5 Hz, 1H), 7.45-7.15 (m, 10H), 6.98 (m, 1H), 4.09 (dd, J = 9.0, 8.5 Hz, 1H),

    3.00-2.90 (m, 1H), 2.80-2.70 (m, 2H), 2.24 (td, J = 15.5, 2.5 Hz, 1H), 1.95 (broad d, J = 13.5

    Hz, 1H), 1.73 (t, J = 13.5 Hz, 1H), 1.46 (s, 9H), 1.25-1.15 (m, 1H), 0.62 (d, J = 7.0 Hz, 3H),

    0.58 (d, J = 6.5 Hz, 3H), 0.30-0.20 (m, 1H); 13C NMR (75 MHz, CDCl3) 205.4 (Cq), 163.1

    (Cq), 144.5 (Cq), 142.9 (CH), 137.1 (Cq), 136.3 (Cq), 135.9 (CH), 130.3 (2CH), 129.0

    (2CH), 128.4 (4CH), 128.3 (CH), 127.3 (CH), 81.1 (Cq), 62.8 (Cq), 56.4 (CH), 36.3 (CH2),

    35.5 (CH), 32.3 (CH2), 31.85 (CH), 31.78 (CH), 28.2 (CH3), 19.6 (CH3), 18.9 (CH3); IR:

    max= 2927, 1702, 1674, 1591, 1366, 1161, 935, 754, 696 cm-1; HRMS (ESI) calcd. For

    C31H36NaO3 [M+Na]+: 479.2562, found: 479.2581; HPLC Analysis: 86% ee [Daicel

    CHIRACEL IA, 2% EtOH/n-heptane, 1mL/min, 300 nm, retention times: 11.3 min (minor)

    and 15.4 min (major)].

    (E)-tert-butyl 7-benzylidene-9-tert-butyl-6-oxo-4-phenylspiro[4.5]-

    dec-1-ene-1-carboxylate 3c. Procedure a (catalyst CyPPh2): 87%

    yield, 90/10 dr; Procedure b (catalyst (S,S)-FerroPHANE): 71%

    yield, 95% ee, 90/10 dr; Pale yellow solid; 1H NMR (500 MHz,

    CDCl3) 7.65 (d, J = 1.5 Hz, 1H), 7.45-7.15 (m, 10H), 6.99 (br, 1H), 4.06 (t, J = 9.0 Hz, 1H),

    2.95 (ddd, J = 18.0, 9.5, 2.0 Hz, 1H), 2.91 (m, 1H), 2.78 (ddd, J = 18.0, 8.0, 3.0 Hz, 1H), 2.21

    (m, 1H), 1.99 (m, 1H), 1.75 (t, J = 13.0 Hz, 1H), 1.47 (s, 9H), 0.60 (s, 9H), 0.33 (m, 1H); 13C

    NMR (75 MHz, CDCl3) 205.4 (Cq), 163.2 (Cq), 144.6 (Cq), 143.0 (CH), 139.3 (Cq), 137.6

    (Cq), 136.3 (Cq), 135.8 (CH), 130.2 (2CH), 129.2 (2CH), 128.5 (4CH), 128.4 (CH), 127.4

    (CH), 81.2 (Cq), 62.9 (Cq), 56.3 (CH), 39.9 (CH), 35.6 (CH2), 32.3 (Cq), 29.9 (CH2), 29.2

    (CH2), 28.3 (CH3), 27.0 (CH3); IR: max= 2965, 1701, 1586, 1365, 1253, 1161, 1105, 758, 691

    cm-1; Melting point: 123-126C; HRMS (ESI) calcd. For C32H38NaO3 [M+Na]+: 493.2719,

    found: 493.2713; HPLC Analysis: 95% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane,

    1ml/min, 300 nm, retention times: 6.5 min (minor) and 8.4 min (major)].

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 10

    (E)-tert-butyl 7-benzylidene-6-oxo-4,9-diphenylspiro[4.5]dec-1-ene-1-

    carboxylate 3d. Procedure a (catalyst CyPPh2): 64% yield, 85/15 dr;

    White solid; 1H NMR (500 MHz, CDCl3) 7.79 (m, 1H), 7.40-6.95 (m,

    15H), 6.82 (d, J = 7.5 Hz, 1H), 4.23 (dd, J = 10.0, 8.0 Hz, 1H), 3.00-

    2.90 (m, 2H), 2.90-2.70 (m, 2H), 2.25 (t, J = 13.5 Hz, 1H), 2.15-2.10

    (m, 1H), 1.65-1.55 (m, 1H), 1.53 (s, 9H); 13C NMR (75 MHz, CDCl3) 204.6 (Cq), 163.0

    (Cq), 145.2 (Cq), 144.4 (Cq), 142.9 (CH), 139.1 (Cq), 136.8 (CH), 136.5 (Cq), 135.9 (Cq),

    130.4 (CH), 128.9 (CH), 128.8 (CH), 128.6 (CH), 128.5 (CH), 127.7 (CH), 126.7 (CH), 126.5

    (CH), 81.3 (Cq), 63.2 (Cq), 56.6 (CH), 37.6 (CH), 37.1 (CH2), 35.3 (CH2), 35.2 (CH2), 28.3

    (CH3); IR: max= 3060, 2979, 1695, 1591, 1338, 1243, 1157, 1122, 945, 750, 692 cm-1;

    HRMS (ESI) calcd. For C34H34NaO3 [M+Na]+: 513.2406, found: 513.2406; HPLC Analysis:

    90% ee [Daicel CHIRACEL IA, 5% EtOH/n-heptane, 1mL/min, 300 nm, retention times: 6.3

    min and 7.3 min]; Melting point: 130-131C.

    (E)-ethyl 9-tert-butyl-7-(4-methoxybenzylidene)-4-(4-

    methoxyphenyl)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2e.

    Procedure b (catalyst (S,S)-FerroPHANE): 91% yield, 93%

    ee, >95/5 dr; Colorless oil; 1H NMR (300 MHz, CDCl3)

    7.63 (d, J = 2.1 Hz, 1H), 7.38 (d, J = 8.7 Hz, 2H), 7.12 (d, J

    = 8.4 Hz, 2H), 6.99 (t, J = 2.4 Hz, 1H), 6.92 (d, J = 6.9 Hz,

    2H), 6.78 (d, J = 8.7 Hz, 2H), 4.20-4.05 (m, 3H), 3.83 (s, 3H), 3.75 (s, 3H), 2.95-2.85 (m,

    2H), 2.76 (ddd, J = 18.3, 8.1, 3.0 Hz, 1H), 2.30-2.20 (m, 1H), 1.96 (dt, J = 13.5, 3.0 Hz, 1H),

    1.70 (t, J = 13.2 Hz, 1H), 1 .24 (t, J = 6.9 Hz, 3H), 0.61 (s, 9H), 0.43 (tt, J = 12.6, 3.0 Hz,

    1H); 13C NMR (75 MHz, CDCl3) 205.2 (Cq), 163.9 (Cq), 159.9 (Cq), 158.9 (Cq), 143.5

    (CH), 143.4 (Cq), 136.1 (CH), 135.2 (Cq), 132.2 (2CH), 131.3 (Cq), 130.1 (2CH), 128.8

    (Cq), 114.0 (2CH), 113.9 (2CH), 62.7 (Cq), 60.5 (CH2), 55.5 (CH3), 55.4 (CH3), 55.0 (CH),

    40.0 (CH), 36.1 (CH2), 32.2 (Cq), 29.8 (CH2), 29.3 (CH2), 27.2 (3CH3), 14.2 (CH3); IR:

    max= 2953, 2358, 1709, 1604, 1509, 1366, 1248, 1162, 1030, 830, 730 cm-1; HRMS (ESI)

    calcd. For C32H38NaO5 [M+Na]+: 525.2617, found: 555.2601; HPLC Analysis: 94% ee

    [Daicel CHIRACEL IA, 5% iPrOH/n-heptane, 1mL/min, 300 nm, retention times: 22.4 min

    (minor) and 43.8 min major)]; []D24 = +355 (c = 1.23, CHCl3).

    OEtOOC

    MeO

    OMe

    Ph

    O

    PhPh

    COOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 11

    (E)-ethyl 9-tert-butyl-7-(4-methylbenzylidene)-6-oxo-4-p-tolyl-

    spiro[4.5]dec-1-ene-1-carboxylate 2f. Procedure b (catalyst (S,S)-

    FerroPHANE): 77% yield, 90% ee, 95/5 dr; White solid; 1H NMR (300 MHz, CDCl3) 7.62 (d, J = 2.1 Hz, 1H), 7.30 (d, J

    = 8.1 Hz, 2H), 7.19 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 8.4 Hz, 2H),

    7.04 (d, J = 8.4 Hz, 2H), 7.01 (t, J = 2.4 Hz, 1H), 4.30-4.00 (m, 3H), 3.00-2.85 (m, 2H),

    2.76(ddd, J = 18.0, 7.8, 3.0 Hz, 1H), 2.37 (s, 3H), 2.29 (s, 3H), 2.25-2.15 (m, 1H), 1.97 (dt, J

    = 13.5, 3.0 Hz, 1H), 1.70 (t, J = 13.2 Hz, 1H), 1.24 (t, J = 7.2 Hz, 3H), 0.58 (s, 9H), 0.37 (tt, J

    = 12.9, 3.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) 205.5 (Cq), 163.9 (Cq), 143.5 (CH), 143.4

    (Cq), 138.6 (Cq), 137.0 (Cq), 136.5 (Cq), 136.1 (CH), 136.0 (Cq), 133.4 (Cq), 130.4 (2CH),

    129.2 (2CH), 129.1 (2CH), 129.0 (2CH), 62.8 (Cq), 60.6 (CH2), 55.5 (CH), 40.0 (CH), 35.9

    (CH2), 32.3 (Cq), 29.9 (CH2), 29.3 (CH2), 27.1 (3CH3), 21.5 (CH3), 21.1 (CH3), 14.2 (CH3);

    IR: max= 2945, 1701, 1670, 1597, 1435, 1367, 1233, 1160, 1093, 1029, 813, 755 cm-1;

    Melting point: 172-173C; HRMS (ESI) calcd. For C32H38NaO3 [M+Na]+: 493.2719, found:

    493.2735; HPLC Analysis: 90% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane,

    1mL/min, 300 nm, retention times: 11.5 min (minor) and 17.9 min major)]; []D24 = +320 (c =

    0.87, CHCl3).

    (E)-ethyl 9-tert-butyl-7-(4-chlorobenzylidene)-4-(4-chloro

    phenyl)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2g. Procedure b

    (catalyst (S,S)-FerroPHANE): 86% yield, 86% ee, >95/5 dr;

    White solid; 1H NMR (300 MHz, CDCl3) 7.57 (d, J = 2.4 Hz,

    1H), 7.36 (d, J = 8.7 Hz, 2H), 7.30 (d, J = 8.7 Hz, 2H), 7.23 (d, J

    = 8.5 Hz, 2H), 7.14 (d, J = 8.5 Hz, 2H), 7.00 (t, 3J = 2.5 Hz, 1H,

    CH2CH=C), 4.20-4.00 (m, 3H), 2.95-2.75 (m, 3H), 2.25 (m, 1H), 1.95 (dt, J = 13.8, 2.7 Hz,

    1H), 1.72 (t, J = 13.2 Hz, 1H), 1.25 (t, J = 7.2 Hz, 3H), 0.59 (s, 9H), 0.29 (tt, J = 12.9, 2.7 Hz,

    1H); 13C NMR (75 MHz, CDCl3) 204.8 (Cq), 163.7 (Cq), 143.3 (CH, Cq), 137.7 (Cq),

    137.5 (Cq), 134.9 (CH), 134.5 (Cq), 134.4 (Cq), 133.2 (Cq), 131.5 (2CH), 130.4 (2CH), 128.8

    (2CH), 128.6 (2CH), 62.8 (Cq), 60.7 (CH2), 54.9 (CH), 40.5 (CH), 35.9 (CH2), 32.3 (Cq),

    29.8 (CH2), 29.2 (CH2), 27.1 (CH3), 14.3 (CH3); IR: max= 2942, 1704, 1587, 1491, 1369,

    1235, 1163, 1089, 1013, 831, 760 cm-1; Melting point: 145-147C; HRMS (ESI) calcd. For

    C30H32NaCl2O3 [M+Na]+: 533.1626, found: 533.1608; HPLC Analysis: 86% ee [Daicel

    CHIRACEL IA, 5% iPrOH/n-heptane, 1mL/min, 300 nm, retention times: 11.6 min (minor)

    and 15.8 min major)]; []D24 = +280 (c = 1.0, CHCl3).

    OEtOOC

    OEtOOC

    Cl

    Cl

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 12

    (E)-ethyl 9-tert-butyl-4-(naphthalen-1-yl)-7-(naphthalen-1-

    ylmethylene)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2h

    Procedure b (catalyst (S,S)-FerroPHANE): 95% yield, 85%

    ee, 95/5 dr; Pale yellow oil; 1H NMR (500 MHz, CDCl3)

    8.14 (d, J = 8.5 Hz, 1H), 7.95 (br, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.79 (dd, J = 12.5, 8.5 Hz,

    2H), 7.72 (d, J = 8.0 Hz, 1H), 7.66 (d, J = 7.0 Hz, 1H), 7.55-7.20 (m, 7H), 7.13 (t, J = 2.5 Hz,

    1H), 6.95 (d, J = 7.0 Hz, 1H), 5.02 (t, J = 9.0 Hz, 1H), 4.30-4.20 (m, 2H), 3.22 (ddd, J = 18.5,

    10.0, 2.0 Hz, 1H), 2.96 (ddd, J = 18.0, 7.5, 3.0 Hz, 1H), 2.28 (dt, J = 14.5, 2.8 Hz, 1H), 2.19

    (dt, J = 14.0, 2.5 Hz, 1H), 1.97 (m, 1H), 1.75 (t, J = 13.0 Hz, 1H), 1.33 (t, J = 7.0 Hz, 3H),

    0.37 (s, 9H), -0.1 (m, 1H); 13C NMR (75 MHz, CDCl3) 206.4 (Cq), 163.9 (Cq), 143.5 (Cq),

    143.2 (CH), 139.4 (Cq), 135.4 (Cq), 134.9 (CH), 134.1 (Cq), 133.6 (Cq), 133.4 (Cq), 132.7

    (Cq), 131.6 (Cq), 128.9 (CH), 128.3 (CH), 128.2 (CH), 126.7 (CH), 126.3 (CH), 126.2 (CH),

    126.1 (CH), 126.0 (CH), 125.9 (CH), 125.4 (CH), 125.3 (CH), 125.0 (CH), 124.5 (CH), 63.5

    (Cq), 60.7 (CH2), 50.0 (CH), 40.9 (CH), 37.8 (CH2), 32.2 (Cq), 31.0 (CH2), 29.1 (CH2), 26.9

    (CH3), 14.4 (CH3); IR: max= 2954, 1704, 1597, 1440, 1366, 1246, 1160, 1046, 907, 777, 728

    cm-1; HRMS (ESI) calcd. For C38H38KO3 [M+K]+: 581.2458, found: 581.2482; HPLC

    Analysis: 81% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane, 1mL/min, 300 nm,

    retention times: 10.9 min (minor) and 18.4 min major)]; []D24 = -20 (c = 1.2, CHCl3).

    (E)-ethyl 9-tert-butyl-4-(naphthalen-2-yl)-7-(naphthalen-2-

    ylmethylene)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2i.

    Procedure b (catalyst (S,S)-FerroPHANE): 72% yield, 90%

    ee, 95/5 dr; White solid; 1H NMR (300 MHz, CDCl3)

    7.90-7.70 (m, 9H), 7.55-7.40 (m, 5H), 7.31 (dd, J = 8.1, 1.5

    Hz, 1H), 7.10 (t, J = 2.7 Hz, 1H), 4.35-4.15 (m, 3H), 3.14

    (ddd, J = 18.0, 9.6, 2.1 Hz, 1H), 2.98 (m, 1H), 2.90 (ddd, J =18.3, 7.8, 3.0 Hz, 1H), 2.40-2.30

    (m, 1H), 2.11 (dt, J = 13.8, 2.7 Hz, 1H), 1.80 (t, J = 12.9 Hz, 1H), 1.30 (t, J = 7.2 Hz, 3H),

    0.41 (s, 9H), 0.31 (dt, J = 12.9, 3.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) 205.4 (Cq), 163.9

    (Cq), 143.6 (CH), 143.4 (Cq), 137.7 (Cq), 136.6 (Cq), 136.2 (CH), 133.7 (Cq), 133.4 (Cq),

    133.2 (Cq), 133.1 (Cq), 132.8 (Cq), 130.1 (CH), 128.4 (CH), 128.0 (3CH), 127.79 (CH),

    127.75 (CH), 127.62 (CH), 127.59 (CH), 127.3 (CH), 126.8 (CH), 126.5 (CH), 126.3 (CH),

    125.9 (CH), 63.2 (Cq), 60.7 (CH2), 56.0 (CH), 40.3 (CH), 36.0 (CH2), 32.1 (Cq), 30.1 (CH2),

    29.4 (CH2), 26.9 (CH3), 14.3 (CH3); IR: max= 2956, 2359, 1706, 1585, 1366, 1241, 1162,

    1097, 855, 818, 746, 668 cm-1; Melting point: 165-166C; HRMS (ESI) calcd. For

    C38H38NaO3 [M+Na]+: 565.2719, found: 565.2736; HPLC Analysis: 90% ee [Daicel

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 13

    CHIRACEL IA, 5% iPrOH/n-heptane, 1mL/min, 300 nm, retention times: 14.8 min (minor)

    and 27.8 min (major)]; []D24 = +343 (c = 0.88, CHCl3).

    (E)-ethyl 9-tert-butyl-4-(furan-2-yl)-7-(furan-2-ylmethylene)-6-

    oxospiro[4.5]dec-1-ene-1-carboxylate 2j. Procedure b (catalyst

    (S,S)-FerroPHANE): 57% yield, 92% ee, 75/25 dr; Yellow oil; 1H

    NMR (300 MHz, CDCl3) 7.54 (d, J = 1.5 Hz, 1H), 7.49 (d, J = 2.4

    Hz, 1H), 7.29 (dd, J = 1.5, 0.6 Hz, 1H), 6.91 (t, J = 2.4 Hz, 1H), 6.62

    (d, J = 3.3 Hz, 1H), 6.49 (dd, J = 3.3, 1.8 Hz, 1H), 6.28 (dd, J = 3.0, 1.8 Hz, 1H), 6.11 (d, J =

    3.0 Hz, 1H), 4.20-4.00 (m, 3H), 3.18 (dt, J = 16.5, 3.0 Hz, 1H), 2.88 (ddd, J = 18.0, 10.5, 3.0

    Hz, 1H), 2.77 (ddd, J = 18.0, 8.1, 3.0 Hz, 1H), 2.31 (ddd, J = 15.9, 13.2, 2.7 Hz, 1H), 2.03 (dt,

    J = 13.8, 2.7 Hz, 1H), 1.65 (t, J = 13.2 Hz, 1H), 1.19 (t, J = 7.2 Hz, 3H), 0.76 (s, 9H), 0.44 (tt,

    J = 12.9, 3.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) 203.6 (Cq), 163.5 (Cq), 153.5 (Cq),

    152.9 (Cq), 144.6 (CH), 143.8 (Cq), 142.6 (CH), 141.4 (CH), 133.1 (Cq), 123.5 (CH), 116.2

    (CH), 112.4 (CH), 110.6 (CH), 108.1 (CH), 62.2 (Cq), 60.6 (CH2), 49.0 (CH), 39.4 (CH),

    34.7 (CH2), 32.3 (Cq), 30.0 (CH2), 29.4 (CH2), 27.2 (CH3), 14.1 (CH3); IR: max= 2960,

    1709, 1670, 1591, 1243, 1103, 735 cm-1; HRMS (ESI) calcd. For C26H30NaO5 [M+Na]+:

    423.2171, found: 423.2176; HPLC Analysis: 92% ee [Daicel CHIRACEL IA, 5% iPrOH/n-

    heptane, 1mL/min, 330 nm, retention times: 22.3 min (minor) and 35.8 min (major)]; []D24 =

    +166 (c = 0.62, CHCl3).

    (E)-ethyl 4-benzylidene-3-oxo-5'-phenylspiro[bicyclo[3.1.0]hexane-2,1'-

    cyclopent[2]ene]-2'-carboxylate 5a. Procedure b (catalyst (S,S)-

    FerroPHANE): 63% yield, 83% ee, 95/5 dr; Orange oil; 1H NMR (500

    MHz, CDCl3) 7.91 (m, 2H), 7.65-7.45 (m, 9H), 7.38 (t, J = 2.7 Hz, 1H),

    4.33 (m, 2H), 4.08 (dd, J = 8.4, 6.0 Hz, 1H), 3.46 (ddd, J = 18.6, 8.4, 2.7 Hz, 1H), 3.06 (ddd,

    J = 18.9, 6.3, 2.7 Hz, 1H), 2.75-2.60 (m, 1H), 1.85-1.75 (m, 1H), 1.39 (t, J = 6.9 Hz, 3H),

    1.17-1.10 (m, 1H), 0.03 (m, 1H); 13C NMR (75 MHz, CDCl3) 209.1 (Cq), 163.9 (Cq), 146.2

    (CH), 142.6 (Cq), 140.4 (Cq), 139.3 (Cq), 135.9 (Cq), 131.1 (CH), 130.1 (2CH), 129.1 (CH),

    128.8 (2CH), 128.7 (2CH), 128.4 (2CH), 126.9 (CH), 67.0 (Cq), 60.6 (CH2), 52.5 (CH), 40.0

    (CH2), 22.3 (CH), 20.2 (CH), 15.9 (CH2), 14.1 (CH3); IR: max= 2928, 1708, 1625, 1493,

    1325, 1263, 1177, 1112, 1028, 755, 692 cm-1; HRMS (ESI) calcd. For C26H24NaO3

    [M+Na]+: 407.1623, found: 407.1634; HPLC Analysis: 86% ee [Daicel CHIRACEL IA,

    10% iPrOH/ n-heptane, 1mL/min, 300 nm, retention times: 6.8 min (major) and 7.8 min

    (minor)]; []D24 = +11 (c = 1.6, CHCl3).

    OEtOOC

    O

    O

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 14

    (E)-ethyl 4-benzylidene-6-methyl-3-oxo-5'-phenylspiro[bicyclo[3.1.0]

    hexane-2,1'-cyclopent[2]ene]-2'-carboxylate 5b. Procedure b (catalyst

    (S,S)-FerroPHANE): 66% yield, 83% ee, 95/5 dr; Orange oil; 1H NMR

    (500 MHz, CDCl3) 7.63 (d, J = 7.5 Hz, 2H), 7.40-7.20 (m, 9H), 7.11 (t,

    J = 2.5 Hz, 1H), 4.08 (m, 2H), 3.77 (dd, J = 9.0, 5.5 Hz, 1H), 3.24 (ddd, J = 19.0, 9.0, 2.5 Hz,

    1H), 2.79 (ddd, J = 19.0, 5.5, 2.5 Hz, 1H), 2.23 (m, 1H), 1.25 (m, 1H), 1.14 (t, J = 7.0 Hz,

    3H), 0.69 (d, J = 6.0 Hz, 3H), 0.13 (m, 1H); 13C NMR (75 MHz, CDCl3) 209.8 (Cq), 163.9

    (Cq), 146.0 (CH), 143.5 (Cq), 140.3 (Cq), 138.9 (Cq), 135.9 (Cq), 130.7 (CH), 130.1 (2CH),

    129.1 (CH), 128.7 (4CH), 128.4 (2CH), 126.9 (CH), 67.9 (Cq), 60.6 (CH2), 52.4 (CH), 40.5

    (CH2), 30.9 (CH), 29.0 (CH), 25.1 (CH) 16 9 (CH3), 14.1 (CH3); IR: max= 2924, 1711, 1627,

    1448, 1264, 1176, 1102, 1027, 732 cm-1; HRMS (ESI) calcd. For C27H26NaO3 [M+Na]+:

    421.1780, found: 421.1786; HPLC Analysis: 83% ee [Daicel CHIRACEL IA, 10% iPrOH/

    n-heptane, 1mL/min, 270 nm, retention times: 7.9 min (major) and 10.9 min (minor)]; []D24

    = +16 (c = 1.5, CHCl3).

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 15

    4) NMR spectra and HPLC analysis

    (E)-ethyl 7-benzylidene-9-methyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 2a 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm

    0.634

    0.647

    0.845

    0.858

    1.256

    1.264

    1.270

    1.278

    1.293

    1.669

    1.696

    1.721

    1.924

    1.930

    1.936

    1.958

    1.963

    2.222

    2.227

    2.232

    2.258

    2.735

    2.741

    2.771

    2.777

    2.782

    2.792

    2.798

    2.813

    2.819

    2.828

    2.834

    2.952

    2.956

    2.972

    2.976

    4.143

    4.159

    4.163

    4.173

    4.178

    4.187

    4.192

    4.201

    4.206

    7.006

    7.011

    7.016

    7.231

    7.237

    7.241

    7.251

    7.255

    7.265

    7.270

    7.282

    7.314

    7.327

    7.333

    7.340

    7.344

    7.378

    7.381

    7.394

    7.404

    7.407

    7.419

    7.671

    7.676

    0.84

    2.74

    3.12

    1.10

    1.00

    0.92

    2.16

    1.02

    2.62

    0.62

    8.80

    0.57

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.255

    21.969

    26.497

    35.725

    36.575

    37.467

    56.086

    60.664

    62.942

    76.750

    77.173

    77.596

    127.492

    128.419

    128.460

    128.500

    128.601

    130.489

    136.071

    136.136

    136.673

    139.094

    143.318

    143.348

    163.837

    205.219

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 16

    HPLC Analysis: Table 2, entry 1: 76% ee [Daicel CHIRACEL IC, 10% iPrOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 17

    (E)-ethyl 7-benzylidene-9-isopropyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 2b 1H NMR (300 MHz, CDCl3):

    8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    0.242

    0.246

    0.537

    0.551

    0.564

    0.577

    1.159

    1.171

    1.231

    1.245

    1.259

    1.661

    1.688

    1.714

    1.913

    1.919

    1.925

    1.946

    2.246

    2.760

    2.766

    2.776

    2.782

    2.790

    2.796

    2.802

    2.812

    2.818

    2.929

    2.933

    2.949

    2.953

    4.099

    4.115

    4.120

    4.127

    4.135

    4.141

    4.149

    4.155

    4.163

    4.170

    4.177

    4.184

    4.191

    4.199

    6.995

    7.000

    7.004

    7.167

    7.196

    7.202

    7.211

    7.222

    7.233

    7.250

    7.275

    7.286

    7.292

    7.298

    7.304

    7.310

    7.315

    7.353

    7.369

    7.376

    7.380

    7.644

    7.649

    1.00

    5.96

    1.17

    3.74

    1.26

    1.01

    1.00

    2.36

    1.18

    3.62

    1.01

    14.11

    1.13

    13C NMR (75 MHz, CDCl3):

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 18

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.238

    18.929

    19.639

    31.747

    31.822

    32.290

    35.812

    36.641

    55.859

    60.598

    62.817

    76.732

    77.155

    77.579

    127.372

    128.424

    128.464

    128.931

    130.396

    136.095

    136.155

    136.979

    139.074

    143.286

    143.469

    163.813

    205.428

    HPLC Analysis: Table 2, entry 2: 82% ee [Daicel CHIRACEL IA, 10% iPrOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 19

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 20

    (E)-ethyl 7-benzylidene-9-tert-butyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 2c

    1H NMR (300 MHz, CDCl3):

    8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    0.270

    0.493

    0.537

    0.641

    1.156

    1.180

    1.194

    1.203

    1.649

    1.693

    1.895

    2.807

    2.848

    2.855

    4.005

    4.038

    4.063

    4.086

    4.101

    4.125

    6.938

    6.945

    6.954

    7.123

    7.149

    7.155

    7.170

    7.181

    7.224

    7.240

    7.252

    7.295

    7.309

    7.563

    7.571

    1.21

    8.48

    4.80

    1.36

    1.05

    1.03

    1.17

    2.00

    3.61

    1.19

    11.07

    1.07

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.248

    27.028

    29.166

    29.937

    32.223

    35.799

    40.214

    55.782

    60.580

    62.950

    76.740

    77.163

    77.587

    127.362

    128.358

    128.433

    128.459

    129.131

    130.214

    135.926

    136.177

    137.407

    139.043

    143.268

    143.558

    163.810

    205.437

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 21

    HPLC Analysis: Table 2, entry 3: 92% ee [Daicel CHIRACEL IC, 10% iPrOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 22

    (E)-ethyl 7-benzylidene-6-oxo-1,9-diphenylspiro[4.5]dec-1-ene-2-carboxylate 2d 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    1.321

    1.335

    1.346

    1.360

    1.564

    1.570

    1.590

    1.596

    1.609

    1.616

    2.122

    2.128

    2.150

    2.200

    2.226

    2.253

    2.787

    2.793

    2.802

    2.808

    2.823

    2.828

    2.838

    2.845

    2.852

    2.878

    2.883

    2.957

    2.974

    2.977

    2.989

    3.010

    3.013

    4.182

    4.197

    4.204

    4.211

    4.218

    4.223

    4.232

    4.237

    4.247

    4.252

    4.259

    4.266

    4.274

    4.280

    4.296

    6.782

    6.796

    7.016

    7.030

    7.143

    7.158

    7.172

    7.198

    7.213

    7.282

    7.340

    7.354

    7.365

    7.368

    7.397

    7.412

    7.780

    7.784

    3.80

    1.22

    1.24

    1.16

    2.34

    2.36

    3.25

    1.86

    1.00

    13.43

    0.74

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.312

    35.180

    35.474

    37.171

    37.847

    56.175

    60.753

    63.295

    76.738

    77.161

    77.584

    126.527

    126.755

    127.692

    128.461

    128.643

    128.797

    128.909

    130.494

    135.823

    136.440

    136.940

    138.929

    143.148

    143.448

    145.080

    163.788

    204.692

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 23

    HPLC Analysis: Table 2, entry 4: 92% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOEt

    OCOOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 24

    (E)-tert-butyl 7-benzylidene-9-methyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 3a

    1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.379

    0.385

    0.391

    0.398

    0.404

    0.637

    0.650

    0.851

    0.864

    0.893

    0.908

    0.921

    1.283

    1.290

    1.310

    1.464

    1.470

    1.490

    1.498

    1.517

    1.667

    1.693

    1.719

    1.913

    1.918

    1.941

    1.946

    2.154

    2.160

    2.185

    2.210

    2.215

    2.733

    2.739

    2.749

    2.755

    2.761

    2.769

    2.785

    2.791

    2.916

    2.919

    2.937

    2.940

    2.952

    2.955

    2.972

    4.088

    4.104

    4.107

    4.123

    6.950

    6.954

    7.173

    7.188

    7.210

    7.215

    7.245

    7.248

    7.282

    7.306

    7.320

    7.391

    7.400

    7.414

    7.425

    7.670

    7.674

    7.693

    1.03

    3.07

    0.81

    0.74

    11.96

    1.32

    0.24

    1.09

    1.24

    2.24

    1.05

    1.00

    0.19

    0.84

    0.17

    13.24

    1.01

    0.20

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.243

    14.327

    21.160

    22.003

    22.818

    26.314

    28.238

    35.429

    36.706

    37.508

    56.548

    60.505

    62.890

    76.741

    77.164

    77.588

    81.197

    127.429

    128.416

    128.443

    128.597

    130.416

    135.891

    136.161

    136.789

    139.267

    142.792

    144.566

    163.080

    171.244

    205.114

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 25

    HPLC Analysis: Table 2, entry 5: 90% ee [Daicel CHIRACEL IA, 5% iPrOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 26

    (E)-tert-butyl 7-benzylidene-9-isopropyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 3b 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.582

    0.596

    0.609

    0.623

    0.759

    0.774

    0.788

    1.194

    1.207

    1.268

    1.280

    1.460

    1.465

    1.500

    1.512

    1.621

    1.679

    1.696

    1.723

    1.750

    1.785

    1.809

    1.939

    1.967

    2.235

    2.751

    2.757

    2.767

    2.773

    2.782

    2.787

    2.792

    2.805

    2.809

    2.924

    2.928

    2.944

    2.948

    2.960

    4.072

    4.090

    4.107

    6.976

    6.980

    6.990

    7.176

    7.192

    7.227

    7.237

    7.246

    7.257

    7.270

    7.272

    7.281

    7.296

    7.322

    7.325

    7.333

    7.337

    7.341

    7.349

    7.395

    7.402

    7.405

    7.417

    7.419

    7.673

    7.678

    7.688

    1.07

    7.22

    3.38

    1.44

    15.64

    2.84

    1.24

    1.17

    3.54

    1.73

    1.00

    0.46

    1.30

    15.33

    1.20

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    18.929

    19.550

    19.591

    19.643

    28.231

    28.259

    31.662

    31.775

    31.854

    32.040

    32.334

    32.488

    33.025

    34.483

    35.556

    36.373

    36.687

    56.351

    57.101

    61.718

    62.773

    76.741

    77.164

    77.588

    81.131

    81.165

    127.218

    127.340

    128.164

    128.353

    128.403

    128.445

    128.545

    128.962

    128.983

    130.337

    130.635

    135.958

    136.201

    136.290

    136.481

    137.087

    139.248

    142.929

    143.078

    144.551

    146.372

    163.111

    163.841

    203.959

    205.391

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 27

    HPLC Analysis: Table 2, entry 6: 86% ee [Daicel CHIRACEL IA, 2% EtOH/n-heptane, 1 mL/min, 300 nm]:

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 28

    (E)-tert-butyl 7-benzylidene-9-tert-butyl-6-oxo-4-phenylspiro[4.5]dec-1-ene-1-carboxylate 3c 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.094

    0.307

    0.333

    0.358

    0.422

    0.467

    0.604

    0.641

    0.753

    0.890

    0.905

    0.918

    0.964

    1.262

    1.267

    1.287

    1.307

    1.324

    1.338

    1.467

    1.512

    1.619

    1.726

    1.753

    1.779

    1.986

    2.013

    2.176

    2.181

    2.206

    2.232

    2.237

    2.753

    2.759

    2.769

    2.775

    2.789

    2.795

    2.805

    2.811

    2.896

    2.926

    2.945

    2.949

    2.962

    2.981

    2.985

    4.045

    4.062

    4.080

    6.988

    7.193

    7.226

    7.239

    7.245

    7.251

    7.261

    7.282

    7.291

    7.329

    7.343

    7.369

    7.383

    7.390

    7.405

    7.415

    7.420

    7.651

    7.654

    0.97

    8.89

    10.44

    1.24

    1.01

    1.00

    1.28

    2.11

    0.84

    0.81

    9.93

    0.73

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    27.023

    28.267

    29.216

    29.967

    32.310

    35.624

    39.923

    56.302

    57.201

    62.967

    76.743

    77.166

    77.590

    81.189

    127.276

    127.366

    128.352

    128.479

    129.051

    129.209

    130.182

    130.633

    135.801

    136.267

    137.571

    139.261

    143.027

    144.552

    163.163

    205.436

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 29

    HPLC Analysis: Table 2, entry 7: 95% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OCOOtBu

    OCOOtBu

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 30

    (E)-ethyl 9-tert-butyl-7-(4-methoxybenzylidene)-4-(4-methoxyphenyl)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2e 1H NMR (300 MHz, CDCl3):

    8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    0.429

    0.435

    0.605

    0.643

    0.748

    1.222

    1.236

    1.251

    1.598

    1.681

    1.708

    1.734

    1.948

    1.975

    2.257

    2.282

    2.759

    2.773

    2.779

    2.789

    2.795

    2.864

    2.868

    2.888

    2.900

    2.904

    2.920

    3.753

    3.776

    3.819

    3.830

    4.069

    4.087

    4.097

    4.104

    4.111

    4.119

    4.133

    4.147

    4.150

    4.165

    4.179

    4.187

    4.194

    4.201

    6.772

    6.790

    6.907

    6.924

    6.993

    6.998

    7.002

    7.108

    7.125

    7.257

    7.371

    7.388

    7.622

    7.625

    1.12

    9.43

    4.41

    1.25

    0.99

    1.03

    1.20

    2.12

    3.05

    3.28

    3.32

    2.11

    2.16

    1.05

    2.06

    2.15

    1.00

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.256

    27.173

    29.359

    29.778

    32.257

    36.113

    40.065

    54.987

    55.431

    55.513

    60.536

    62.722

    76.744

    77.167

    77.591

    113.885

    113.999

    128.828

    130.072

    131.343

    132.240

    135.241

    136.100

    143.463

    143.565

    158.968

    159.880

    163.898

    205.222

    OEtOOC

    MeO

    OMe

    OEtOOC

    MeO

    OMe

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 31

    HPLC Analysis: Table 3, entry 1: 94% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OEtOOC

    MeO

    OMe

    OEtOOC

    MeO

    OMe

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 32

    (E)-ethyl 9-tert-butyl-7-(4-methylbenzylidene)-6-oxo-4-p-tolylspiro[4.5]dec-1-ene-1-carboxylate 2f 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    1.261

    1.270

    1.284

    1.304

    1.310

    1.702

    1.728

    1.754

    1.979

    2.006

    2.224

    2.229

    2.254

    2.280

    2.285

    2.311

    2.337

    2.372

    2.392

    2.762

    2.768

    2.778

    2.784

    2.799

    2.804

    2.814

    2.820

    2.918

    2.924

    2.947

    2.961

    2.980

    2.984

    4.079

    4.096

    4.114

    4.130

    4.137

    4.144

    4.151

    4.180

    4.199

    4.207

    4.214

    4.221

    4.228

    4.235

    7.031

    7.059

    7.075

    7.105

    7.121

    7.208

    7.224

    7.282

    7.316

    7.332

    7.645

    0.84

    7.28

    3.31

    1.06

    0.83

    0.96

    2.69

    2.76

    1.00

    1.69

    2.76

    0.85

    3.59

    1.69

    1.68

    0.85

    13C NMR (75 MHz, CDCl3):

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 33

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.259

    21.087

    21.499

    27.107

    29.305

    29.895

    32.253

    35.914

    40.015

    55.467

    60.559

    62.847

    76.740

    77.163

    77.587

    129.013

    129.063

    129.207

    130.448

    130.754

    133.385

    136.022

    136.137

    136.530

    136.965

    138.565

    143.362

    143.643

    163.894

    205.470

    HPLC Analysis: Table 3, entry 2: 90% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 34

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 35

    (E)-ethyl 9-tert-butyl-7-(4-chlorobenzylidene)-4-(4-chlorophenyl)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2g 1H NMR (300 MHz, CDCl3):

    7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    0.251

    0.284

    0.294

    0.303

    0.327

    0.337

    0.525

    1.158

    1.181

    1.205

    1.612

    1.657

    1.701

    1.850

    1.860

    1.869

    1.896

    1.906

    1.915

    2.126

    2.136

    2.177

    2.185

    2.219

    2.229

    2.666

    2.675

    2.692

    2.702

    2.726

    2.736

    2.752

    2.762

    2.784

    2.791

    2.815

    2.822

    3.981

    4.011

    4.028

    4.040

    4.052

    4.064

    4.070

    4.088

    4.094

    4.107

    4.111

    4.118

    4.131

    4.142

    4.154

    6.916

    6.924

    6.932

    7.052

    7.080

    7.141

    7.149

    7.171

    7.177

    7.190

    7.220

    7.249

    7.276

    7.298

    7.305

    7.504

    7.512

    1.19

    8.45

    4.68

    1.13

    0.96

    0.97

    3.05

    3.41

    0.95

    8.57

    1.00

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.276

    27.084

    29.221

    29.792

    32.316

    35.983

    40.502

    54.949

    60.717

    62.791

    76.738

    77.161

    77.585

    128.594

    128.789

    130.404

    131.540

    133.205

    134.446

    134.497

    134.947

    137.513

    137.656

    143.321

    163.690

    204.767

    OEtOOC

    Cl

    Cl

    OEtOOC

    Cl

    Cl

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 36

    HPLC Analysis: Table 3, entry 3: 86% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OEtOOC

    Cl

    Cl

    OEtOOC

    Cl

    Cl

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 37

    (E)-ethyl 9-tert-butyl-4-(naphthalen-1-yl)-7-(naphthalen-1-ylmethylene)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2h 1H NMR (300 MHz, CDCl3):

    8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    -0.091

    0.311

    0.370

    0.520

    1.311

    1.325

    1.339

    1.720

    1.747

    1.773

    1.966

    2.184

    2.212

    2.276

    2.305

    2.963

    4.206

    4.221

    4.228

    4.242

    4.263

    4.277

    4.284

    5.008

    5.024

    5.043

    6.947

    6.961

    7.127

    7.132

    7.137

    7.247

    7.260

    7.296

    7.299

    7.310

    7.312

    7.319

    7.327

    7.329

    7.335

    7.349

    7.410

    7.424

    7.440

    7.454

    7.456

    7.462

    7.478

    7.487

    7.489

    7.493

    7.504

    7.506

    7.520

    7.653

    7.667

    7.709

    7.725

    7.775

    7.791

    7.799

    7.816

    7.841

    7.857

    7.954

    7.957

    8.135

    8.152

    1.00

    8.98

    3.53

    1.16

    0.98

    2.12

    1.09

    1.03

    2.23

    1.01

    0.94

    1.02

    7.95

    5.42

    1.02

    1.06

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.336

    26.931

    29.077

    30.946

    32.184

    37.771

    40.896

    49.955

    60.705

    63.469

    76.728

    77.152

    77.575

    124.496

    125.060

    125.250

    125.375

    125.884

    125.971

    126.125

    126.195

    126.274

    126.409

    126.722

    128.009

    128.228

    128.312

    128.861

    131.592

    132.655

    133.378

    133.592

    134.079

    134.905

    135.409

    139.374

    143.223

    143.497

    163.914

    206.335

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 38

    HPLC Analysis: Table 3, entry 4: 85% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 39

    (E)-ethyl 9-tert-butyl-4-(naphthalen-2-yl)-7-(naphthalen-2-ylmethylene)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2i 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.312

    0.338

    0.364

    0.423

    0.490

    0.701

    1.298

    1.312

    1.326

    1.781

    1.807

    1.834

    2.102

    2.129

    2.337

    2.901

    2.906

    2.916

    2.922

    2.937

    2.942

    2.952

    2.958

    2.977

    3.006

    3.125

    3.144

    3.158

    3.161

    4.180

    4.194

    4.201

    4.216

    4.231

    4.246

    4.260

    4.268

    4.282

    4.314

    4.332

    4.348

    7.115

    7.281

    7.320

    7.337

    7.444

    7.452

    7.460

    7.462

    7.493

    7.505

    7.513

    7.520

    7.523

    7.527

    7.530

    7.723

    7.745

    7.761

    7.769

    7.781

    7.788

    7.799

    7.811

    7.818

    7.830

    7.841

    7.857

    7.880

    1.46

    9.02

    3.30

    1.11

    1.04

    0.96

    2.08

    1.00

    2.84

    0.77

    1.22

    4.37

    8.13

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.246

    14.304

    22.818

    26.889

    29.359

    29.486

    29.785

    29.827

    30.105

    32.053

    32.134

    35.976

    40.343

    56.001

    60.665

    63.165

    76.738

    77.161

    77.584

    125.878

    126.343

    126.467

    126.801

    127.319

    127.589

    127.620

    127.754

    127.799

    127.965

    128.432

    130.089

    132.777

    133.051

    133.239

    133.382

    133.708

    136.161

    136.618

    137.663

    143.439

    143.589

    163.881

    205.384

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 40

    HPLC Analysis: Table 3, entry 5: 90% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    OEtOOC

    OEtOOC

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 41

    (E)-ethyl 9-tert-butyl-4-(furan-2-yl)-7-(furan-2-ylmethylene)-6-oxospiro[4.5]dec-1-ene-1-carboxylate 2j 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.432

    0.442

    0.453

    0.761

    1.167

    1.190

    1.214

    1.602

    1.647

    1.691

    2.000

    2.009

    2.019

    2.045

    2.055

    2.254

    2.264

    2.298

    2.308

    2.317

    2.779

    2.789

    2.806

    2.816

    2.829

    2.836

    2.864

    2.871

    3.147

    3.156

    3.211

    4.050

    4.062

    4.074

    4.086

    4.098

    4.110

    4.112

    4.127

    4.136

    4.149

    4.160

    4.172

    6.104

    6.114

    6.274

    6.280

    6.284

    6.290

    6.486

    6.492

    6.497

    6.503

    6.619

    6.630

    6.906

    6.914

    6.922

    7.262

    7.272

    7.281

    7.284

    7.287

    7.289

    7.486

    7.494

    7.538

    7.543

    7.552

    1.13

    8.12

    3.93

    0.94

    0.94

    1.01

    1.24

    1.07

    1.00

    3.13

    0.87

    1.11

    0.99

    0.94

    0.86

    0.96

    1.94

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.161

    27.199

    29.352

    30.028

    32.254

    34.699

    39.385

    48.961

    60.621

    62.158

    76.742

    77.165

    77.589

    108.069

    110.574

    112.356

    116.211

    123.467

    133.146

    141.387

    142.579

    143.792

    144.563

    152.909

    153.464

    163.521

    203.580

    OEtOOC

    O

    O

    OEtOOC

    O

    O

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 42

    HPLC Analysis: Table 3, entry 6: 92% ee [Daicel CHIRACEL IA, 5% iPrOH /n-heptane, 1 mL/min, 330 nm]:

    OEtOOC

    O

    O

    OEtOOC

    O

    O

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 43

    (E)-ethyl 4-benzylidene-3-oxo-5'-phenylspiro[bicyclo[3.1.0]hexane-2,1'-cyclopent[2]ene]-2'-carboxylate 5a 1H NMR (300 MHz, CDCl3):

    8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

    0.000

    0.017

    1.096

    1.115

    1.123

    1.142

    1.149

    1.169

    1.363

    1.387

    1.410

    1.502

    1.508

    1.525

    1.762

    1.778

    1.785

    1.789

    1.801

    1.805

    1.812

    2.724

    2.737

    3.027

    3.039

    3.081

    3.089

    3.101

    3.110

    3.410

    3.419

    3.439

    3.448

    3.501

    3.510

    4.054

    4.075

    4.083

    4.103

    4.299

    4.307

    4.323

    4.331

    4.347

    4.355

    4.370

    4.378

    7.369

    7.378

    7.387

    7.463

    7.470

    7.476

    7.486

    7.498

    7.507

    7.516

    7.528

    7.542

    7.556

    7.575

    7.580

    7.590

    7.615

    7.637

    7.644

    7.897

    7.920

    7.925

    1.00

    1.19

    3.03

    1.07

    1.00

    1.03

    1.01

    1.02

    2.02

    1.01

    9.39

    2.09

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.114

    15.916

    20.215

    22.270

    40.023

    52.533

    60.611

    66.968

    76.739

    77.162

    77.585

    126.909

    128.366

    128.676

    128.787

    129.091

    130.147

    131.112

    135.864

    139.341

    140.406

    142.634

    146.157

    163.855

    209.115

    O

    Ph

    Ph

    COOEt

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 44

    HPLC Analysis: product 5a: 86% ee [Daicel CHIRACEL IA, 10% iPrOH /n-heptane, 1 mL/min, 300 nm]:

    O

    Ph

    Ph

    COOEt

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 45

    (E)-ethyl 4-benzylidene-6-methyl-3-oxo-5'-phenylspiro[bicyclo[3.1.0]hexane-2,1'-cyclopent[2]ene]-2'-carboxylate 5b 1H NMR (300 MHz, CDCl3):

    0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

    0.106

    0.113

    0.117

    0.120

    0.125

    0.133

    0.685

    0.697

    1.122

    1.136

    1.150

    1.237

    1.246

    1.251

    1.259

    2.223

    2.230

    2.237

    2.242

    2.767

    2.772

    2.778

    2.783

    2.805

    2.810

    2.816

    2.821

    3.211

    3.216

    3.229

    3.234

    3.249

    3.254

    3.267

    3.272

    3.755

    3.766

    3.773

    3.784

    4.051

    4.059

    4.068

    4.073

    4.082

    4.087

    4.096

    4.101

    4.111

    4.118

    7.102

    7.107

    7.112

    7.203

    7.206

    7.217

    7.232

    7.253

    7.259

    7.267

    7.275

    7.289

    7.305

    7.310

    7.325

    7.350

    7.366

    7.380

    7.621

    7.636

    1.00

    3.05

    3.18

    1.59

    1.02

    1.06

    1.03

    1.00

    2.14

    0.93

    10.27

    1.97

    13C NMR (75 MHz, CDCl3):

    210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

    14.128

    16.987

    25.051

    29.047

    30.952

    40.539

    52.421

    60.618

    67.862

    76.744

    77.167

    77.590

    126.873

    128.404

    128.703

    129.057

    130.066

    130.675

    135.992

    138.976

    140.261

    143.487

    146.001

    163.914

    209.758

    O

    Ph

    Ph

    COOEt

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

  • 46

    HPLC Analysis: product 5b: 83% ee [Daicel CHIRACEL IA, 10% iPrOH /n-heptane, 1 mL/min, 270 nm]:

    O

    Ph

    Ph

    COOEt

    O

    Ph

    Ph

    COOEt

    Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

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