highly enantioselective carbon-carbon bond …supporting information page no 1) experimental...

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Highly enantioselective carbon-carbon bond formation by Cu-catalyzed asymmetric [2, 3]-sigmatropic rearrangement: Application to the syntheses of seven-membered oxacycles and six-membered carbocycles Gullapalli Kumaraswamy*a, Kadivendi Sadaiah a, Duggirala Subrahmanya Ramakrishnaa, Police Nareshb, Balasubramanian Sridharc and Bharatam Jagadeeshb

aOrganic Division-III, Telephone: + 91-40-27193154; Fax: + 91-40-27193275;

e-mail: [email protected] bNMR Division,

cLaboratory of X-ray crystallography, Indian Institute of Chemical Technology, Hyderabad, 500 007, India

Supporting Information

Page No 1) EXPERIMENTAL PROCEDURE & SPCTRAL DATA 2-18 a) Compounds generated by using (1R, 2R)-1, 2-diphenylethane-1, 2-diol 2-14 b) Compounds generated by using (R)-phenylethylene glycol 14-16 c) Cyclopropanation 16-18 2) 1H, 13C and NOESY NMR SPECTRA 19-59 a) Compounds generated by using (1R, 2R)-1, 2-diphenylethane-1, 2-diol 19-49 b) Compounds generated by using (R)-phenylethylene glycol 50-54 c) Cyclopropanation 55-59 3) SPCTRAL DATA 60-61 a) Compounds generated by using (1S, 2S)-1, 2-diphenylethane-1, 2-diol 4) 1H, 13C and NOESY NMR SPECTRA 62-69 a) Compounds generated by using (1S, 2S)-1, 2-diphenylethane-1, 2-diol 5) Chiral HPLC Analysis 70-81 6) X-ray Crystallographic analysis of 10 82

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General Procedures: 1H NMR spectra were recorded at 200, 300, 400, 500 & 600 M Hz and 13C NMR 50, 75, 100, 125 & 150 M Hz, in CDCl3. IR (FT-IR) Spectrometer, measured as KBr pellets or as films between KBr plates. Mass spectral data were compiled using MS (ESI), HRMS mass spectrometers. Optical rotations recorded on HORIBA high sensitive polarimeter, 10mL cell. The diastereomeric purity of the sigmatropic rearrangement products 2, 3, 6a and 7a and cyclopropination product 10 was determined by chiral HPLC (Instrument SPD-10A SHIMADZU, Chiral ADH column and nHexane, IPA and Ethanol as mobile phase).Column chromatography carried out with silica gel, grade 60-120, 100-200 and 230-400 mesh. Starting materials: CH2Cl2 was distilled from P2O5, THF from sodium benzophenone ketyl. All other chemicals used were commercially available. All reactions were conducted under an atmosphere of nitrogen (IOLAR Grade I). Organic extracts were dried over anhydrous Na2SO4.

1) EXPERIMENTAL PROCEDURE & SPCTRAL DATA Procedure for (Z)-4-methoxy but-2-en-1-ol:

HO OMe A solution of (Z)-2-butene-1,4-diol (56 mL, 0.68 mol) in 1,4-dioxane (680 mL) was added potassium hydroxide (133 g, 2.37 mol) and H2O (20 mL). Upon heating the resulting mixture upto 70 °C, added dimethyl sulphate (65 ml, 0.68 mol) drop wise over a period of 1 h. The combined contents then stirred for 2 h at 80 °C and cooled to rt, filtered the slurry. The organic layer was separated and concentrated under vacuum. The residue was purified through column chromatography (silica gel 60-120mesh) using hexane:EtOAc (9:1) to give the product (Z)-4-methoxy but-2-en-1-ol as light yellow liquid ( 38 g. 55%). 1H NMR (200 MHz, CDCl3): δ 5.81-5.74 (m, 1H), 5.67-5.59 (m, 1H), 4.14 (d, J = 6.0 Hz, 2H), 3.97 (d, J = 6.0 Hz, 2H), 3.33 (s, 3H), 2.65 (br. s, 1H); IR (Neat): 3423, 2924, 2855, 1727, 1457, 1377, 1189, 1094 cm-1; MS (ESIMS) m/z 103 (M+H+). General Procedure A Step1: To a DCM (200 mL) solution of (Z) - 4-methoxy but-2-en-1-ol (13.34 g, 130.83 mmol) was added Et3N (20.92 mL, 150.37 mmol). To this mixture methanesulphonyl chloride (10.7 mL, 137.21 mmol) was added slowly at 0 °C. Then, the mixture was allowed over a period of 2h at 0 °C to rt. The organic layer was washed with water (2 X 100 mL) and contents were dried over anhydrous Na2SO4. The resultant solution was filtered and concentrated under reduced pressure. The crude product was used for next step without purification.

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Step2: To a dry THF (500 mL) solution of 1, 2-diol (93.45 mmol) was added portion wise NaH (60% dispersion in mineral oil) (4.1 g, 102.79 mmol) at 0 °C. After 30 min, mesylate of (Z)-4-methoxy but-2-en-1-ol in THF (50 mL) was added slowly maintaining same temperature. The resulting mixture was warmed to rt and stirred overnight. The reaction mixture was quenched with water till the mixture become clear. This mixture was extracted with ethyl acetate (4 x 200 mL). The combined organic layers were washed with brine (2 X 100 mL) and dried over anhydrous Na2SO4. Filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silicagel (100-200 mesh) column chromatography eluting with hexane:EtOAc furnished the pure product as oily compound . General Procedure B To a xylene (170 mL) solution of 2-(4-methoxybut-2-enyloxy)-phenylethanol (40.27 mmol) was added 2, 2, 6-Trimethyl-4H-1, 3-dioxine-4-one (5.85 mL, 44.29 mmol) at rt. This mixture was allowed to reflux for 30 min. Then, xylene was distilled from the reaction mixture. The crude product was subjected to silicagel (60-120mesh) column chromatography eluting with EtOAc in hexane furnished the pure product as yellow oil. General Procedure C To an acetonitrile (30 mL) solution of 3-oxobutanoate (10.86 mmol), Hunig base was added. To this mixture a predissolved solution of Tosyl azide (2.33g, 14.12 mmol) in acetonitrile (10 mL) was added. This mixture was allowed to stir at rt over a period of 3 h, then, a solution of LiOH (1.49g, 35.47 mmol) in H2O (15 mL) was added and stirred for 6 h at rt. The organic layer was separated and aqueous layer was extracted with Ethyl acetate (4 X 20 mL). To the combined organic layers brine (2 X 30 mL) wash was given, and dried over anhydrous Na2SO4. The resultant solution was filtered and concentrated under reduced pressure. The crude product was subjected to silicagel (60-120mesh) column chromatography eluting with EtOAc in hexane furnished the pure product as yellow viscous liquid. General Procedure D A solution of diazoacetate (2.73 mmol) in DCM (60 mL) was added using a syringe pump to a solution of Tetrakis (acetonitrile) copper(I) hexaflorophosphate ( 51 mg, 5 mol%) in DCM (60 mL) under reflux condition for 5 h. The reaction mixture was allowed to rt, then solvent was removed under reduced pressure. The crude product was subjected to silicagel (100-200 mesh) column chromatography eluting with EtOAc in hexane furnished the pure products syn and anti 6:4 ratio and 2-(4-methoxybut-2-enyloxy) phenylethanol (15%) also recovered.

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a) Compounds generated by using (1R, 2R)-1, 2-diphenylethane-1, 2-diol Procedure for (1R, 2R, Z)-2-(4-methoxybut-2-enyloxy)-1, 2-diphenylethanol (8a):

OHPh

Ph OOMe

(8a) This compound was prepared according to the general procedure A, as color less oil (Yield 68%). [α]D

24 +3.8 (c 0.110, CHCl3); 1H NMR (200 MHz, CDCl3): δ 7.19-7.10 (m, 6H), 6.98-6.93 (m, 4H), 5.81-5.62 (m, 2H), 4.60 (d, J = 8.1 Hz, 1H), 4.20 (d, J = 8.1 Hz, 1H), 3.98-3.93 (m, 2H), 3.79 (d, J = 5.1 Hz, 2H), 3.22 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 142.0, 133.5, 128.3, 128.2, 127.8, 127.2, 126.7, 86.8, 85.3, 78.4, 29.6, 27.1.IR (Neat) 3466, 3062, 3031, 2926, 2877, 1731, 1454, 1190, 701 cm-1; MS (ESIMS) m/z 299 (M+H+), 281,197, 103, 85. Procedure for (1R, 2R)-2-((Z)-4-methoxybut-2-enyloxy)-1, 2-diphenylethyl 3-oxobutanoate:

OPh

Ph OOMe

O

O

This compound was prepared according to the general procedure B. (Yield 85%). [α]D

24 -29.2 (c 0.126, CHCl3); 1H NMR (200 MHz, CDCl3): δ 7.20-7.13 (m, 6H), 7.05-7.00 (m, 4H), 5.93-5.89 (d, J = 8.0 Hz, 1H), 5.66-5.60 (m, 2H), 4.53-4.50 (d, J = 7.3 Hz, 1H), 3.91 (m, 2H), 3.76 (d, J = 5.1 Hz, 2H), 3.42 (s, 2H), 3.21 (s, 3H), 2.21(s, 3H); 13C NMR (75 MHz, CDCl3): δ 200.2, 166.0, 137.0, 129.5, 128.8, 128.0, 127.9, 127.7, 127.4, 83.2, 79.3, 67.9, 64.4, 57.8, 50.3; IR (Neat): 3453, 2925, 1717, 1360, 1201, 1151, 763, 700 cm-1 ; MS (ESIMS): m/z 405 (M+Na+), 400, 384, 180. Procedure for (1R, 2R)-2-((Z)-4-methoxybut-2-enyloxy)-1, 2-diphenylethyl 2-diazoacetate (5a):

OPh

Ph OOMeON2

(5a) This compound was prepared according to the general procedure C, as yellow oil (Yield 95%).

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[α]D24 -2.4 (c 0.018, CHCl3); 1H NMR (200 MHz, CDCl3): δ 7.19-7.11 (m, 6H), 7.03-

6.98 (m, 4H), 5.94 (d, J = 7.3 Hz, 1H), 5.66-5.61 (m, 2H), 4.51 (d, J = 7.3 Hz, 1H), 3.99-3.88 (m, 2H), 3.77 (d, J = 4.4 Hz, 2H), 3.21 (s, 3H);13C NMR (75 MHz, CDCl3): δ 129.5, 127.9, 127.8, 127.3, 83.2, 78.5, 68.0, 64.5, 57.8, 46.3, 29.6, 29.0. IR (Neat): 3443, 3031, 2925, 2113, 1729, 1453, 1378, 1188, 1090.5, 702.7 cm-1; MS (ESIMS): m/z 367 (M+H+), 281, 211, 143, 85; HRMS (ESIMS): Calculated for C21H22N2O4Na, 389.1471, Found 389.1483. Procedure for (2R, 3R, 6R, 7R)-6-methoxy-2, 3-diphenyl-7-vinyl-1, 4-dioxocan-5-one (6a) and (2R, 3R, 6S, 7R)-6-methoxy-2, 3-diphenyl-7-vinyl-1, 4-dioxocan-5-one (7a): These compounds were prepared according to the general procedure D. Syn was white solid (yield 41%) and anti was a color less oil (yield 27%),(1R, 2R, Z)-2-(4-methoxybut-2-enyloxy)-1, 2- (yield 15%) also recovered.

O

OPh

Ph

O

OMe

Syn (6a) M.P 120 oC: [α]D

24 -74.0 (c 0.010, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.29-7.17(m, 6H), 7.10 (d, J = 6.5 Hz, 2H), 6.98 (d, J = 6.5 Hz, 2H), 6.13 (ddd, J1 = 17.0 Hz, J2 = 11.0 Hz, J3 = 8.7 Hz 1H), 5.94 (d, J = 9.0 Hz, 1H), 5.29-5.26 (m, 2H), 4.37 (d, J = 9.7 Hz, 1H), 4.22 (dd, J1 = 6.5, J2 = 11.6 Hz, 1H), 4.16 (d, J = 5.8 Hz, 1H), 3.93 (d, J = 10.3 Hz, 1H), 3.51 (s, 3H), 3.30-3.21 (m, 1H);13C NMR (100 MHz, CDCl3): δ 174.1, 137.0, 135.1, 133.7, 128.6, 128.2, 128.0, 127.5, 127.3, 118.4, 96.1, 86.9, 80.0, 74.0, 58.4, 50.3. IR (KBr): 3473, 3084, 2938, 2890, 1745, 1454, 1209, 1116, 986, 698 cm-1; MS (ESIMS): m/z 338. (M+H+), 321, 242, 197; HRMS (ESIMS): Calculated for C21H22O4Na, 361.1415, Found 361.1415.

O

OPh

PhO

OMe

Anti (7a) [α]D

24 -126.0 (c 0.091, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.25-7.24 (m, 3H), 7.22-7.20 (m, 3H), 7.13-7.11 (m, 2H), 7.00-6.99 (m, 2H), 6.02 (d, J = 9.2, 1H), 5.82 (ddd, J1 =17.4 Hz, J2 =10.4 Hz, J3 = 8.4 Hz, 1H), 5.22 (td, J = 17.3 Hz, J = 1.4, 2H), 5.18 (td, J1 = 10.4 Hz, J2 = 1.4 Hz, 1H), 4.35 (d, J = 9.2 Hz, 1H), 4.16 (t, J = 10.6 Hz, 1H), 4.05 (dd, J1

O

O

H

H

H

H

H

O

HH

H

HPh

Ph

MeO a

b

d

c

e f

g

h

i

O

O

HHO

H H

H

H

H

HH

Ph

OMe

Ph

ab

c

d

ef

h

g i

6

=10.7 Hz, J2= 3.01 Hz, 1H), 4.02 (d, J = 3.2 Hz, 1H), 3.48 (s, 3H), 3.18-3.13 (m, 1H); 13C NMR (100 MHz, CDCl3): δ 175.4, 137.2, 134.1, 128.4, 128.2, 128.1, 127.5, 127.4, 117.8, 91.7, 86.7, 81.7, 73.6, 52.5; IR (Neat): 3448, 3033, 2928, 1743, 1454, 1226, 1094, 762, 699 cm-1; MS (ESIMS): m/z 339 (M+H+), 297289, 242.2, 197. HRMS (ESIMS) Calculated for C21H22O4Na, 361.1411, Found 361.1427 Procedure for (R)-2-((R)-2-(tert-butyldimethylsilyloxy)-1-methoxyethyl) but-3-en-1-ol (12):

OTBDMSMeO

HO

(12) To a suspension of LAH (327 mg, 8.61mmol) in dry THF (40 mL), a predissolved solution of 6a in dry THF (30mL) (1.94 g, 5.74 mmol) was added slowly at 0 °C. Stirring was continued at 0oC- rt for 2 h. The reaction was quenched with 10%NaOH slowly at 0 °C and allowed to stir at rt for 45 min. Then the reaction mixture was decanted and concentrated to get the crude product which was taken for next step without any purification. To a Dry DCM (70 mL) solution of above alcohol and Imidazole (1.25 g, 18.36 mmol) TBDMSCl (922 mg, 6.11mmol) was added at 0 °C and stirred for 4 h. To the resultant mixture, water (50 mL) was added and organic layer was separated. The aqueous layer was extracted (3 X 20mL) with DCM dried over anhydrous Na2SO4. Filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was used for next step without any purification. A 250 mL two necks RB was fitted with a neck ammonia condenser with guard tube and another neck was fitted with stopper, 60-80 mL of ammonia was condensed. Then Li granules (280 mg) were added slowly. Blue colour was appeared. Then stopper was replaced by septum. To this blue solution, above silyl ether in THF (30 mL) was added slowly. After 30 min the reaction mixture was quenched with solid NH4Cl slowly. Then ammonia condenser was removed and allowed to rt to remove the excess Liquid ammonia. To this mixture water was added and extracted with Ethyl acetate (3 X 30mL). The combined organic layers were dried over anhydrous Na2SO4. Filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silicagel (60-120mesh) column chromatography eluting with hexane:EtOAc (94:6) furnished the pure product as color less liquid (1.21 g, 81%) for three steps. [α]D

24 -2.4 (c 0.035, CHCl3); 1H NMR (300 MHz, CDCl3): δ 5.71 (ddd, J1 = 8.3 Hz, J2 = 10.6 Hz, J3 = 18.9 Hz, 1H), 5.17-5.12 (m, 2H), 3.74 (dd, J1 = 3.8 Hz, J2 = 10.6 Hz, 1H), 3.70-3.67 (m, 1H), 3.63-3.57 (m, 2H), 3.46 (s, 3H), 3.32-3.27 (m, 1H), 2.51-2.42 (m, 1H), 0.90 (s, 9H), 0.05 (s, 6H);13C NMR (75 MHz, CDCl3): δ 135.7, 118.32, 83.36, 63.81, 61.18, 57.95, 47.57, 25.81, -5.51; IR (Neat): 3426, 2928, 2857, 1465, 1253, 1092, 837, 776 cm-1; MS (ESIMS) 261 (M+H+), 243, 175; HRMS (ESIMS): Calculated for C13H28O3NaSi, 283.1699, Found 283.1701.

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Procedure for (R)-2-((S)-2-(tert-butyldimethylsilyloxy)-1-methoxyethyl) but-3-en-1-ol (12’):

OTBDMSMeO

HO

(12’) This compound was prepared according to the above procedure, starting material is 7a instead of 6a, as color less liquid yield (81%) for three steps. [α]D

24 -11.6 (c 0.036, CDCl3); 1H NMR (300 MHz, CDCl3): δ 5.72 (ddd, J1 = 9.1 Hz, J2 = 10.6 Hz, J3 = 19.6 Hz, 1H), 5.17-5.12 (m, 2H), 3.78-3.57 (m, 4H), 3.47 (s, 3H), 3.32-3.27 (m, 1H), 2.59 (br.s, 1H), 2.51-2.42 (m, 1H), 0.90 (s, 9H), 0.06 (s, 6H);13C NMR (100 MHz, CDCl3): δ 136.1, 117.6, 84.5, 64.1, 63.2, 58.5, 47.4, 25.8, 18.2, -5.5; IR (Neat): 3382, 2925, 2855, 1461, 1079, 759 cm-1; MS (ESIMS): m/z 283 (M+Na+), 261 (M+H+), 198, 182; HRMS (ESIMS): Calculated for C13H28O3NaSi, 283.1709, Found 283.1721. Procedure for ((2R, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-enyloxy) (tert-butyl) dimethylsilane:

OTBDMSMeO

BnO

To a solution of 12 (2.05 g, 7.88 mmol) in Dry THF(40 mL), NaH 60%(dispersion in mineral oil) (473 mg, 11.82 mmoL) was added portions wise at 0 °C and stirred for 15 min. To the above stirred solution BnBr (1.1 mL, 10.14 mmol) was added slowly. Stirring was continued at 0oC- rt for 6 h. To this reaction mixture water (30 mL) was added then extracted with Ethyl acetate (3 X 30mL). The combined organic layers were dried over anhydrous Na2SO4, filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silicagel (60-120 mesh) column chromatography eluting with EtOAc 5% in hexane furnished the pure product as color less liquid (2.23 g, 94 %) 1H NMR (300 MHz, CDCl3): δ 7.32-7.20 (m, 5H), 5.87-5.75 (m, 1H), 5.12-5.05 (m, 2H), 4.47 (d, J = 1.5 Hz, 2H), 3.70 (dd, J1 = 3.0 Hz, J2 = 10.6 Hz, 1H), 3.63-3.49 (m, 3H), 3.40 (s, 3H), 3.32-3.26 (m, 1H), 2.54-2.46 (m, 1H), 0.88 (s, 9H), 0.03 (s, 6H);13C NMR (75 MHz, CDCl3): δ 137.3, 128.2, 116.9, 82.0, 73.0, 70.6, 63.8, 58.8, 46.0, 25.9, 18.2, -5.4; IR (Neat): 3421, 2925, 2856, 1719, 1456, 1274, 1098, 710 cm-1; MS (ESIMS): m/z 351 (M+H+), 259, 237, 202; HRMS (ESIMS): Calculated for C20H34O3NaSi, 373.2174, found 373.2187

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Procedure for ((2S, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-enyloxy)(tert-butyl) dimethylsilane:

OTBDMSMeO

BnO

This compound was prepared according to the above procedure, starting material is 12’ instead of 12, as color less liquid yield (94 %). [α]D

24 +4.6 (c 0.014, CHCl3); 1H NMR (200 MHz CDCl3): δ 7.33-7.24 (m, 5H), 5.90-5.72 (m, 1H), 5.14-5.05 (m, 2H), 4.47 (s, 2H), 3.75-3.47 (m, 5H), 3.40 (s, 3H), 3.33-3.25 (m, 1H), 2.57-2.44 (m, 1H), 0.89 (s, 9H), 0.03 (s, 6H);13C NMR (75 MHz, CDCl3): δ 129.3, 128.5, 126.5, 116.9, 83.1, 73.0, 70.5, 65.6, 63.7, 57.8, 45.1, 26.8, 25.0, 17.9, -6.3; IR (Neat): 2927, 2856, 1724, 1460, 1272, 1105, 838 cm-1 ; MS (ESIMS): m/z 273 (M+Na+), 351 (M+H+), 242; HRMS (ESIMS): Calculated for C20H34O3NaSi, 373.2174, found 373.2182 Procedure for (2R, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-en-1-ol (13):

OHMeO

BnO

(13) To the Stirred solution of silyl ether (1.63g 4.68mmol) in Methanol (35 mL), PTSA (89 mg 0.46 mmol) was added at 0 oC. Stirring was continued at 0oC- rt for 2 h, then solid NaHCO3 (50 mg) was added to the reaction mixture. After 10 min reaction mixture was filtered. Filtrate was concentrated and purified by silicagel (60-120 mesh) column chromatography eluting with EtOAc 10% in hexane, as color less oil (1.03 g, 94%) [α]D

24 -25.2 (c 0.012, CHCl3); 1H NMR (200 MHz CDCl3): δ 7.30-7.25 (m, 5H), 5.90-5.72 (m, 1H), 5.17-5.08 (m, 2H), 4.49 (s, 2H), 3.72-3.46 (m, 5H), 3.39 (s, 3H), 2.65-2.52 (m, 1H), 2.07 (br.s, 1H);13C NMR (75 MHz, CDCl3): δ 136.3, 128.3, 127.5, 117.4, 81.3, 73.2, 70.3, 61.0, 58.0, 45.7; IR (Neat): 3444, 3069, 3029, 2925, 2857, 1455, 1361, 1208, 1091, 752, 698 cm-1 ; MS (ESIMS): m/z 237 (M+H+),186, 97, 95, 91, 69; HRMS (ESIMS): Calculated for C14H20O3Na, 259.1310, Found 259.1305 Procedure for (2S, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-en-1-ol (13’):

OHMeO

BnO

(13’)

9

This compound was prepared according to the above procedure, as color less oil yield (94 %). [α]D

24 +11.2 (c 0.016, CHCl3); 1H NMR (300MHz CDCl3): δ 7.32-7.20 (m, 5H), 5.86-5.74 (m, 1H), 5.15-5.07 (m, 2H), 4.48 (s, 2H), 3.70-3.42 (m, 4H), 3.40-3.22 (m, 4H), 2.62-2.54 (m, 1H);13C NMR (75 MHz, CDCl3): δ 136.3, 128.3, 127.6, 117.4, 81.3, 73.2, 70.2, 61.6, 58.0, 45.7; IR (Neat): 3446, 2925, 2858, 1456, 1362, 1093 cm-1: MS (ESIMS): m/z 259 (M+Na+), 237 (M+H+),202, 186; HRMS (ESIMS): Calculated for C14H20O3Na, 259.1310, Found 259.1316. Procedure for (((R)-2-((R)-2-(allyloxy)-1-methoxyethyl) but-3-enyloxy) methyl) benzene (14): BnO

OMeO

(14) A solution of 13 (150 mg, 0.635 mmol) in Dry THF(5 mL), NaH 60% (dispersion in mineral oil)(33 mg, 0.825 mmol) was added portions wise at 0 °C and stirred for 15 min. To the above stirred solution allyl bromide (85µL, 0.98 mmol) was added slowly. Stirring was continued at 0oC- rt over a period of 6 h. The reaction was quenched with water, then extract with ethyl acetate (4 X 10mL). The combined organic layers were dried over anhydrousNa2SO4.Filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silica gel (60-120 mesh) column chromatography eluting with EtOAc 5% in hexane furnished the pure product as color less liquid (150 mg, 86%). [α]D

24 -14.5 (c 0.020, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.33-7.20 (m, 5H), 5.92-5.73 (m, 2H), 5.28-5.06 (m, 4H), 4.48 (s, 2H), 3.94 (d J = 5.3 Hz, 2H), 3.64-3.35 (m, 8H), 2.59-2.51 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 136.9, 134.8, 128.2, 127.5, 117.1, 116.7, 80.2, 73.0, 72.2, 70.4, 58.4, 46.1; IR (Neat): 3020, 2402, 1722, 1216, 1094, 759 cm-1; MS (ESIMS): 277 (M+H+); HRMS (ESIMS): Calculated for C17H24O3Na, 299.1617, Found 299.1627. Procedure for (((R)-2-((S)-2-(allyloxy)-1-methoxyethyl) but-3-enyloxy) methyl) benzene (14’): BnO

OMeO

(14’) This compound was prepared according to the above procedure, starting material is 13’ instead of 13, as color less liquid yield (86 %) [α]D

24 +8.7 (c 0.020, CHCl3); 1H NMR (300 MHz CDCl3): δ 7.32-7.20 (m, 5H), 5.92-5.75 (m, 2H), 5.26-5.06 (m, 4H), 4.48 (s, 2H), 3.95(d, J = 5.3 Hz, 2H), 3.64-3.36 (m, 8H), 2.59-2.51 (m, 1H); 13C NMR (50 MHz, CDCl3): δ 138.4, 136.8, 134.7, 128.2, 127.4, 127.3, 117.0, 116.7, 80.2, 73.0, 72.2, 70.5, 70.4, 58.4, 46.1; IR (Neat): 3021, 2404, 1721,

10

1216, 1094, 759 cm-1; MS (ESIMS): m/z 299 (M+Na+), 294 (M+NH4+), 277 (M+H+), 180;

HRMS (ESIMS): Calculated for C17H24O3Na, 299.1617, Found 299.1628. Procedure for oxacycles (15 & 16):

O

BnO

MeO

OO

(15) To a stirred solution of 14 (170 mg, 0.98 mmol) in DCM (120 mL), Grubbs (II) catalyst (42 mg, 0.049 mmol) was added and stirred at reflux for 1 h. Then solvent was removed under reduced pressure and the crude product was dissolved in ethyl acetate (2.5 mL). In another flask, a suspension of NaIO4 (139 mg, 0.652 mmol) in H2O (0.3 mL)was treated with CeCl3.7H2O (37 mg, 0.098 mmol) and heated gently until suspension was bright yellow, at this point the suspension was diluted with MeCN (2 mL) and cooled to 0 °C. To the yellow suspension metathesis solution was added and stirred at 0 °C until oxidation was complete (10-20 min). The reaction was quenched with solid Na2SO3 and Na2SO4 and after stirring for 10 min the solution was filtered through celite (1 cm plug).Celite was washed with EtOAc (3 X 5 mL).The filtrate was concentrated under reduced pressure and the crude product was dissolved in DCM (10 mL), then CSA (23 mg, 0.1 mmol) and 2, 2 DMP (0.24 mL) was added at 0 °C and stirred for overnight at rt. Then solvent was removed under reduced pressure. The crude product was subjected to silica gel (60-120 mesh) column chromatography to afford 15 & 16 as clear oil 115 mg of 15 and 77 mg of 16, total yield 61%. [α]D

24 + 2.4 (c 0.032, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.35-7.27 (m, 5H), 7.36 (m, 4H), 7.29 (m, 1H), 4.59 (dd, J =6.7 Hz, J = 9.7 Hz, 1H), 4.55 (s, 2H), 4.24 (ddd, J1 = 6.7 Hz, J2 =10.5 Hz, J3 =4.1Hz, 1H), 4.06 (dd, J1 = 11.2 Hz, J2 =2.8 Hz, 1H), 3.90 (dd, J1 = 8.4 Hz, J2 = 2.5 Hz, 1H), 3.85 (dd, J1 =12.2 Hz, J2= 4.1 Hz, 1H), 3.70 (dd, J1 = 1.9 Hz, J2 = 8.4 Hz, 1H), 3.34 (dd, J1 =12.2 Hz, J2 =10.5 Hz, H), 3.38 (s, 3H), 3.24 (m, H), 3.21 (m, H), 1.96 (m, H), 1.39 (s, 3H), 1.35 (s, 3H);13C NMR (100 MHz, CDCl3): δ 138.8, 128.2, 127.4, 107.8, 76.3, 76.1, 75.1, 74.5, 73.1, 69.7, 67.2, 58.9, 46.8, 27.6, 24.7;IR (Neat): 2930, 2859, 1457, 1385, 1105, 758 cm-1; Mass (ESIMS): 345(M+Na+), 305, 205, 116; HRMS (ESIMS): Calculated for C18H26O5Na, 345.1677, Found 345.1663.

O

BnO

MeO

OO

(16)

O

HH

O

O

CH3

H

H

HH

OCH2

MeO

H

H

H

HPh

CH3

a

ab

c

d

e

ef

g

g

1

1 1

11

[α]D24 + 54.5 (c 0.026, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.35-7.27 (m, 5H), 4.76

(dd, J1= 7.9 Hz, J2 = 1.6 Hz, 1H), 4.56 (d, J = 4.0Hz, 2H), 4.17 (m, 2H), 4.01 (dd, J1 = 13.7 Hz, J2 =2.9 Hz, 1H), 3.89 (dd, J1= 9.1 Hz, J2 = 4.6, 1H), 3.84 (dd, J1 =12.2 Hz, J2 = 4.1 Hz, 1H), 3.65 (dd, J1 = 9.4 Hz, J2 = 9.1 Hz, 1H), 3.51 (m, 1H), 3.40 (dd, J1 = 13.7 Hz, J2 = 2.2 Hz, 1H) 3.34 (s, 3H), 3.19 (dd, J1 = 12.1Hz, J2 = 9.1 Hz, 1H), 2.18 (m, 1H), 1.49 (s, 3H), 1.35 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 138.8, 128.2, 127.4, 107.8, 76.3, 76.1, 75.1, 74.3, 73.1, 69.7, 67.2, 58.9, 46.8, 27.5, 24.7; IR (Neat): 2930, 2859, 1457, 1385, 1105, 758 cm-1; MS (ESIMS): 345 (M+Na+), 305, 205, 116; HRMS (ESIMS): Calculated for C18H26O5Na, 345.1677, Found 345.1661. Procedure for oxacycles (17 & 18):

O

BnO

MeO

OO

(17) These compound were prepared according to the above procedure, starting material is 14’ instead of 14, yield (61 %) [α]D

24 -1.8 (c 0.028, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.35-7.26 (m, 5H), 4.58 (dd, J1 = 6.7 Hz, J2 = 9.7 Hz, 1H), 4.55 (s, 2H), 4.05 (dd, J1 = 11.4 Hz, J2 = 2.9 Hz, 1H), 3.90 (dd, J1 = 8.5 Hz, J2 = 2.4 Hz, 1H), 3.84 (dd, J1 = 12.2 Hz, J2 = 4.1 Hz, 1H), 3.70 (dd, J1 = 2.0 Hz, J2 = 8.5 Hz, 1H), 3.34 (dd, J1 =12.2 Hz, J2 =10.5 Hz, 1H), 3.38 (s, 3H), 3.24 (m, H), 3.21 (m, H), 1.96 (m, H), 1.39 (s, 3H), 1.35 (s, 3H);13C NMR (100 MHz, CDCl3): δ 128.2, 127.4, 127.4, 107.9, 76.3, 76.1, 75.1, 74.3, 73.1, 69.7, 67.2, 58.9, 46.8, 27.5, 24.8; IR (Neat): 2930, 2859, 1457, 1385, 1105, 758 cm-1: MS (ESIMS): 345 (M+Na+), 305, 205, 116; HRMS (ESIMS): Calculated for C18H26O5Na, 345.1675, Found 345.1684.

O

BnO

MeO

OO

(18) [α]D

24 -55.2 (c 0.020, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.35-7.26 (m, 5H), 4.58 (dd, J1 = 6.7 Hz, J2=9.7 Hz, 1H), 4.55 (s, 2H), 4.05 (dd, J1 = 11.4 Hz, J2 = 2.9 Hz, 1H), 3.90 (dd, J1 = 8.5 Hz, J2 = 2.4 Hz, 1H), 3.84 (dd, J1 = 12.2 Hz, J2 = 4.1 Hz, 1H), 3.70 (dd, J1 = 2.0 Hz, J2 = 8.5 Hz, 1H), 3.34 (dd, J1 =12.2 Hz, J2 = 10.5 Hz, 1H), 3.38 (s, 3H), 3.24 (m, H), 3.21 (m, H), 1.96 (m, H), 1.39 (s, 3H), 1.35 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 138.5, 128.3, 127.5, 107.4, 77.5, 76.9, 74.2, 73.2, 73.2, 72.6, 68.9, 58.8, 45.0, 26.4, 24.3; IR (Neat): 2930, 2859, 1457, 1385, 1105, 758 cm-1; MS (ESIMS) 345(M+Na+), 305, 205, 116; HRMS (ESIMS): Calculated for C18H26O5Na, 345.1677, Found 345.1663.

O

HH

HH

H

HH

HO

CH2

H

H

CH3 CH3

O

O

MeO

Pha

bc

d

e

f

ge

g

a

1

1

1

12

Procedure for (2R, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-enal (19): BnO

HMeO

O (19) To the mixture of alcohol 13 (550 mg, 2.33 mmol), IBX (716 mg), dry DMSO (2 mL) dry DCM (25 mL) was added at rt. This mixture was allowed to stir at rt for 8 h. Then solvent was removed under reduced pressure. The crude product was subjected to silica gel (60-120 mesh) column chromatography to afford pure aldehyde as clear liquid (490 mg, 90%). [α]D

24 -17.6 (c 0.017, CHCl3); 1H NMR (300MHz CDCl3): δ, 9.62(s, 1H), 7.32-7.22(m, 5H), 5.84-5.72 (m, 1H), 5.19-5.12 (m, 2H), 4.44 (d J=4.5, 2H), 3.62-3.54 (m, 2H), 3.46-3.42 (m, 4H), 2.91-2.82 (m, 1H); 13C NMR (75 MHz): δ 203.4, 134.6, 128.3, 127.7, 118.0, 86.3, 73.0, 68.6, 59.2, 46.6; IR (Neat): 3433, 3066, 2925, 2861, 1727, 1642, 1454, 1364, 1172, 1101, 742, 700 cm-1.

Procedure for (2S, 3R)-3-(benzyloxymethyl)-2-methoxypent-4-enal (19’): BnO

HMeO

O (19’) This compound was prepared according to the above same procedure, starting material is 13’ instead of 13, as color less oil yield (90 %) [α]D

24 -9.0 (c 0.014, CHCl3); 1H NMR (200 MHz, CDCl3): δ 9.62 (s, 1H),7.30-7.22 (m, 5H), 5.78 (ddd, J1=8.1 Hz, J2 = 10.3 Hz, J3 = 18.4 Hz, 1H), 5.21-5.11 (m, 2H), 4.44 (d, J = 2.9 Hz, 2H), 3.64-3.53 (m, 2H), 3.48-3.40 (m, 4H), 2.93-2.80 (m, 1H);13C NMR (75 MHz, CDCl3): δ 202.1, 134.8, 128.2, 127.4, 117.8, 96.2, 86.3, 73.0, 68.7, 59.1, 46.8; IR (Neat): 2925, 2858, 1731, 1455, 1197, 1097, 740 cm-1. Procedure for (5R, 6R)-6-(benzyloxymethyl)-5-methoxyocta-1, 7-dien-4-ol (20): BnO

MeOOH

(20) A mixture of AgOTf (0.036 mmol) and (S)-BINAP (0.036 mmol) was dissolved in dry THF (1 mL) under N2 atmosphere and exclusion of direct light, and stirred at 20 oC for 10 min. To the resulting solution was added a THF solution (1 mL) of aldehyde 19 (0.363 mmol) and then allyltributyltin (0.363 mmol) was added dropwise at -20 oC. The mixture

13

was stirred for 8 h at this temperature and treated with a mixture of 1 N HCl (2 mL) and solid KF (0.18 g) at ambient temperature for 30 min. The resulting precipitate was filtered and the filtrate was separated and the aqs layer was extracted with ethyl acetate (3 X 10 mL), the combined organic layers were dried over anhydrousNa2SO4, filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silicagel (230-400 mesh) column chromatography eluting with EtOAc 5% in hexane furnished the pure product as a color less oil 61 % yield (diasteomeric ratio 49 mg and 12 mg). [α]D

24 -16.7 (c 0.010, CHCl3); 1H NMR (200 MHz, CDCl3): δ 7.36-7.21 (m, 5H), 5.96-5.75 (m, 2H), 5.16-5.06 (m, 4H), 4.52 (d, J = 2.2 Hz, 2H), 3.72-3.61 (m, 2H), 3.60-3.49 (m, 1H), 3.42 (s, 3H), 3.22 (t, J = 5.1 Hz, 1H), 2.71-2.59 (m, 2H), 2.42-2.30 (m, 1H);13C NMR (75 MHz, CDCl3): δ 137.3, 135.3, 128.4, 127.7, 117.4, 116.7, 85.0, 73.3, 71.1, 70.0, 60.1, 45.6, 37.4, 27.8, 26.8, 17.5, 13.6; MS (ESIMS): 277 (M+H+), 294(M+NH4

+), 299 (M+Na+); HRMS (ESIMS): Calculated for C17H24O3Na 299.1623, found 299.1617. Procedure for (5S, 6R)-6-(benzyloxymethyl)-5-methoxyocta-1, 7-dien-4-ol (20’): BnO

MeOOH

20' This compound was prepared according to the above procedure, starting material is 19’ instead of 19, as color less oil with same yield and diastereomeric ratio. [α]D

24 +15.4 (c 0.006, CHCl3); 1H NMR (200 MHz, CDCl3): δ 7.36-7.21 (m, 5H), 5.95-5.75 (m, 2H), 5.15-5.05 (m, 4H), 4.50 (d, J = 2.2 Hz, 2H), 3.73-3.18 (m, 7H), 2.70-2.58 (m, 2H), 2.34-2.29 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 137.3, 135.3, 128.4, 127.7, 117.4, 116.7, 85.0, 73.3, 73.3, 70.0, 60.1, 45.6, 37.4, 29.7, 27.8, 26.8, 17.5, 13.6; MS (ESIMS): 277(M+H+), 294(M+NH4

+), 299 (M+Na+); HRMS (ESIMS): Calculated for C17H24O3Na 299.1623, found 299.1627. Procedure for carbocycle (21): BnO

MeOOH(21)

To a stirred solution of 20 (50 mg,0.18 mmol) in DCM (20 mL) Grubbs (II) catalyst (5 mg,0.0054 mmol) was added and stirred at reflux for 45 min. The solvent was removed under reduced pressure and the crude product was purified by silicagel (60-120 mesh) column chromatography eluting with EtOAc 12% in hexane furnished the pure product 35 mg (yield 78 %) as oily liquid. [α]D

24 +77.0 (c 0.006, CHCl3); 1H NMR (500 MHz, CDCl3): δ, 7.36-7.26 (m, 5H), 5.66-5.58 (m, 2H), 4.54 (dd, J1 = 12.4 Hz, J2 =29.3 Hz, 2H), 4.15-4.13(m, 1H), 3.57-3.49 (m,

14

2H), 3.40 (dd, J1 =2.2 Hz, J2 =7.3 Hz, 1H), 2.62-2.58 (m, 1H), 2.35-2.27 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 138.4, 128.3, 127.6, 126.6, 124.4, 96.1, 79.4, 73.1, 70.7, 64.5, 56.9, 38.8, 31.3; MS (ESIMS): 249 (M+H+), 266 (M+NH4

+), 299; HRMS (ESIMS): Calculated for C15H20O3Na 271.1310, found 271.1324. Procedure for carbocycle (22): BnO

MeOOH

(22) This compound was prepared according to the above procedure, starting material is 20’ instead of 20, as oily liquid with same yield. [α]D

24 -23.3 (c , 0.002, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.36-7.27 (m, 5H), 5.64-5.54 (m, 2H), 4.55 (dd J1=12.5, J2=25.5, 2H), 3.86-3.81 (m, 1H), 3.63-3.54 (m, 2H), 3.49 (s, 3H), 3.24 (t, J = 8.3 Hz, 1H), 2.72 (br.s, 1H), 2.52-2.39 (m, 2H), 2.16-2.09 (m, 1H); MS (ESIMS): 249 (M+H+), 266 (M+NH4

+), 299; HRMS (ESIMS): Calculated for C15H20O3Na 271.1310, found 271.1332. b) Compounds generated by using (R)-phenylethylene glycol Procedure for (R, Z)-2-(4-methoxybut-2-enyloxy)-1-phenylethanol(4):

OHPh

OOMe

(4) This compound was prepared according to the general procedure A as color less oil(yield 53.4 %). [α]D

24 +35.0 (c 0.039, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.36-7.25 (m, 5H), 5.76-5.65 (m, 2H), 4.83 (dd, J1 = 3.0 Hz, J2 = 8.9 Hz, 1H), 4.12-4.11 (m, 2H), 3.98-3.93 (m, 2H), 3.56 (dd, J1 = 3.2 Hz, J2 = 9.6 Hz, 1H), 3.39 (t, J = 9.1 Hz, 1H), 3.29 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 129.4, 129.0, 128.4, 128.2, 127.6, 126.8, 126.0, 75.7, 72.6, 66.6, 57.9; IR (Neat): 3466, 3062, 3031, 2926, 2877, 1731, 1454, 1190, 701 cm-1; MS (ESIMS): 245(M+Na+), 85. Procedure for (R, Z)-2-(4-methoxybut-2-enyloxy)-1-phenylethyl 3-oxobutanoate:

OPh

OOMeO

O

H

H

H

H

H

OH

H

H

HH

MeO

OCH2

Ph

a

b

c

d

e

f

g

hi

15

This compound was prepared according to the general procedure B, (yield 79.9 %) as yellow oil. [α]D

24 +33.0 (c 0.056, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.40-7.30 (m, 5H), 5.99 (dd, J1 =3.8 Hz, J2 =8.3 Hz, 1H),4.74-5.61 (m, 2H), 4.13-4.06 (m, 2H), 3.98-3.94 (m, 2H), 3.74 (dd, J1 = 8.3 Hz, J2 = 11.3 Hz, 1H), 3.64-3.58 (m, 1H),3.46 (s, 2H), 3.31 (s, 3H), 2.25 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 166.2, 129.5, 128.7, 128.4, 128.3, 126.8, 126.5, 78.6, 75.2, 72.4, 67.9, 66.6, 64.3, 57.825, 50.1, 29.7; IR (Neat): 3453, 2925, 1717, 1360, 1201, 1151, 763, 700 cm-1; MS (ESIMS) 329(M+Na+). Procedure for (R, Z)-2-(4-methoxybut-2-enyloxy)-1-phenylethyl 2-diazoacetate(1):

OPh

OOMeON2

(1) This compound was prepared according to the general procedure C, as light yellow oil (yield 79.1 %).[α]D

24 +13.6 (c 0.068, CHCl3); 1H NMR (300 MHz CDCl3): δ 7.37-7.26 (m, 5H), 5.98 (dd, J1 = 3.8 Hz, J2 = 8.3 Hz, 1H), 5.71-5.61 (m, 2H), 4.79 (br.s, 1H), 4.11-4.01 (m, 2H), 3.96-3.88 (m, 2H), 3.70 (dd, J1 = 7.6 Hz, J2 = 10.6 Hz, 1H), 3.61-3.56 (m, 1H),3.28 (s, 3H); 13C NMR (75 MHz, CDCl3): δ, 137.3, 129.6, 128.8, 128.4, 128.2, 126.5, 78.9, 74.6, 72.6, 68.0, 66.6, 64.3, 46.3; IR (Neat): 3443, 3031, 2925, 2113, 1729, 1453, 1378, 1188, 1090.5, 702.7 cm-1; MS (ESIMS): 313(M+Na+);HRMS (ESIMS): Calculated for C15H18N2O4Na, 313.1164, Found 313.1167. Procedure for (3R, 6R, 7R)-6-methoxy-3-phenyl-7-vinyl-1, 4-dioxocan-5-one (2) and (3R, 6S, 7R)-6-methoxy-3-phenyl-7-vinyl-1, 4-dioxocan-5-one (3): These compounds were prepared according to the general procedure D. Syn (yield 41 %) and anti (yield 27 %) as a color less oil and (R, Z)-2-(4-methoxybut-2-enyloxy)-1-phenylethanol (yield 15 %) also recovered.

O

O

Ph

O

OMe

Syn (2) [α]D

24 +30.0 (c 0.003, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.40-7.33 (m, 5H), 6.27 (m, 1H), 6.00-5.84 (m, 1H), 5.24-5.19 (m, 2H), 4.11-4.07 (m, 2H)3.96-3.85 (m, 1H), 3.75-3.70 (m, 1H), 3.50-3.43 (m, 4H), 3.12-3.04 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 135.2, 133.4, 128.6, 126.4, 118.4, 80.4, 58.3, 50.2, 49.8.IR (Neat) 3448, 3033, 2928, 1743, 1454, 1226, 1094, 762, 699 cm-1; MS (ESIMS) 285.5(M+Na+);HRMS (ESIMS): Calculated for C15H18O4Na, 285.1102, Found 285.1107.

16

O

O

Ph

O

OMe

Anti (3) [α]D

24 +72.50 (c 0.002, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.38-7.25 (m, 5H), 5.74 (ddd, J1 =8.5 Hz, J2 = 10.2 Hz, J3 = 17.4 Hz, 1H), 5.24-5.14 (m, 2H), 4.04-3.79 (m, 4H), 3.45 (s, 3H), 3.34 (dd, J1 = 10.39 Hz, J2 = 12.09 Hz, 1H), 3.07-2.95 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 134.2, 128.7, 126.3, 117.8, 84.6, 81.4, 79.2, 74.4, 72.8, 58.3, 53.3; IR (Neat): 3448, 3033, 2928, 1743, 1454, 1226, 1094, 762, 699 cm-1; MS (ESIMS): 285.5 (M+Na+);HRMS (ESIMS): Calculated for C15H18O4Na, 285.1102, Found 285.1099. c) Cyclopropanation Procedure for (1R, 2R)-2-(allyloxy)-1, 2-diphenylethanol (11):

OPh

OHPh (11) To a solution of (1R, 2R)-1, 2-diphenylethane-1, 2-diol diol (2.7g, 12.62 mmol) in THF (25mL) was added NaH (60 % disersion in mineral oil) (600 mg, 15.14 mmol) portions wise at 0 oC. To this stirred mixture allyl bromide (1.3mL, 15.14mmol) was added dropwise at same temparature. This mixture was allowed to stir 0 °C – rt for overnight. The reaction mixture was quenched with water till the mixture become clear. This mixture was extracted with Ethyl acetate (4 x 20 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered the contents and concentrated under reduced pressure yielded crude product. The crude product was subjected to silicagel (60-120 mesh) column chromatography eluting with EtOAc 8 % in hexane furnished the pure product as colorless viscous liquid (2.56g, 80%). [α]D

25 +45.2 ˚ (c 0.021, CHCl3 ); 1H NMR (300 MHz, CDCl3): δ 7.17-7.10 (m, 6H), 6.97-6.93 (m, 4H), 5.95-5.82 (m,1H), 5.26-5.14 (m, 2H), 4.62 (d, J = 8.3Hz, 1H), 4.22 (d , J = 8.3 Hz, 1H), 3.97 (dd , J1 = 5.3, J2 = 12.8 Hz, 1H), 3.80 (dd, J1 = 6.0, J2 = 12.8 Hz, 1H), 3.48 (s, 1H); 13C NMR (75 MHz, CDCl3): δ 134.2, 128.1, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.4, 127.2, 117.3, 86.7, 78.5, 69.7; IR (Neat): 3461, 2869, 1722, 1452, 1078, 763, 762, 700 cm-1; HRMS (ESIMS): calculated for C17H18O2Na, 277.1204, found 277.1202.

17

Procedure for (1R, 2R)-2-(allyloxy)-1, 2-diphenylethyl-3-oxobutanoate:

OPh

OPh

O

O

This compound was prepared according to the general procedure B. as yellow liquid (Yield 80 %).[α]D

25 -32.0 ˚ (c 0.012 , CHCl3 ); 1H NMR (300 MHz, CDCl3): δ 7.17-7.11 (m, 6H), 7.03-7.00 (m, 4H), 5.93(d, J = 8.3 Hz, 1H), 5.89-5.73 (m, 1H), 5.22-5.07 (m,2H), 4.53 (d, J = 7.5 Hz, 1H), 3.94 (dd, J1 = 4.5, J2 = 12.8 Hz, 1H), 3.76 (dd, J1 = 6.0, J2 = 13.6 Hz, 1H), 3.41 (s, 2H) 2.20 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 200.4, 166.0, 134.3, 128.3, 128.2, 128.1, 128.0, 127.8, 127.7, 127.6, 127.4, 127.3, 116.7, 83.2, 79.4, 69.6, 50.3, 29.8; IR (Neat): 3447, 2925, 1743, 1718, 1238, 1148, 1075, 701 cm-1; HRMS (ESIMS): calculated for C21H22O4Na, 361.1415, found 361.1412. Procedure for (1R, 2R)-2-(allyloxy)-1.2-diphenylethyl 2-diazoacetate (9):

OPh

OPh

ON

N (9) This compound was prepared according to the general procedure C. as light yellow oil (Yield 90 %). [α]D

25 +18.0 ˚ (c 0.030, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.22-7.16 (m, 6H), 7.06-7.04 (m, 4H), 6.00 (d, J = 6.8 Hz, 1H), 5.89-5.77 (m, 1H), 5.31 -5.14 (m, 2H), 4.79 (s,1H), 4.57 (d, J = 6.8 Hz, 1H), 4.01 (dd, J1 = 4.5, J2 = 12.8 Hz, 1H), 3.79 (dd, J1 = 6.0, J2 = 13.6 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ137.3, 134.4, 128.1, 127.9, 127.7, 127.3, 127.2, 116.5, 83.0, 78.5, 69.6, 46.3; HRMS (ESIMS): calculated for C19H18N2O3Na, 345.1215, found 345.1211. Procedure for (1S, 4R, 5R, 8R)-4, 5-diphenyl-3, 6-dioxa – bicycle [6.1.0] nonan – 2 – one (10):

O

OPh

Ph

O (10)

O

OH

H

H

H

H

O HPh

Ph HH

a b

c

d

e e

b1

1

f

18

A solution of diazoacetate 9 (2.73 mmol) in DCM (60 mL) was added by syringe pump to a solution of Tetrakis (acetonitrile) copper (I) hexaflorophosphate (51 mg, 5 mol %) in DCM (60 mL) under reflux condition for 5 h. The reaction mixture was allowed to rt, then solvent was removed under reduced pressure. The crude product was subjected to silicagel (100-200 mesh) column chromatography eluting with EtOAc in hexane furnished the pure product as white solid. (Yield 50 %) and the alcohol (1R, 2R)-2-(allyloxy)-1, 2-diphenylethanol (yield 15%) also recovered. Mp 118˚C; [α]D

25 -26.5 ˚ (c 0.010, CHCl3 ); 1H NMR (300 MHz, CDCl3): δ 7.25-7.21 (m, 6H), 7.05-6.99 (m, 4H), 5.89 ( d, J = 9.82 Hz, 1H), 4.79 ( d, J = 9.1 Hz, 1H), 4.29-4.26 (m, 1H), 3.75-3.69 (m, 1H), 1.98-1.89 (m, 2H), 1.78 (q, J = 5.3 Hz, 1H), 1.36-1.31 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 176.4, 138.0, 136.3, 128.3, 127.3, 127.1, 93.6, 85.0, 75.9, 24.3, 19.2, 18.0; IR (KBr): 3031, 2924, 1709, 1265, 1079, 1002, 759, 699 cm-1; HRMS (ESIMS): calculated for C19H18O3Na, 3317.1153, found 317.1159.

19

2) 1H, 13C and NOESY NMR SPECTRA a) Compounds generated by using (1R, 2R)-1, 2-diphenylethane-1, 2-diol

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

OHPh

Ph OOMe

Compound (8a) 1H NMR 200 MHz, CDCl3.

3030404050506060707080809090100100110110120120130130140140150150160160

OHPh

Ph OOMe

Compound (8a) 13C NMR 75 MHz, CDCl3.

20

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

OPh

Ph OOMeO

O

Compound 1H NMR 300 MHz, CDCl3.

20203030404050506060707080809090100100110110120120130130140140150150160160170170180180190190200200

OPh

R1 OOMe

O

O

Compound 13C NMR 75 MHz, CDCl3.

21

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

OPh

Ph OOMeON2


20203030404050506060707080809090100100110110120120130130

OPh

Ph OOMeON2


22

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

O

OPh

PhO

OMe+


50506060707080809090100100110110120120130130140140150150160160170170

O

OPh

PhO

OMe+


23

Compound (6a) NOESY

24

0.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

60

19 2010 10

2312 13

2335

11

O

OPh

PhO

OMe


50506060707080809090100100110110120120130130140140150150160160170170

O

OPh

PhO

OMe

Compound (7a) 13 NMR 100 MHz, CDCl3.

25

Compound (7a) NOESY

26

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

OTBDMSMeO

HO

Compound (12) 1H NMR 300 MHz, CDCl3.

-10-1000101020203030404050506060707080809090100100110110120120130130140140

OTBDMSMeO

HO

Compound (12) 13C NMR 75 MHz, CDCl3.

27

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

12

26

4

39

13 1209

124

8

OTBDMSMeO

HO

Compound (13’) 1H NMR 300 MHz, CDCl3.

00101020203030404050506060707080809090100100110110120120130130

OTBDMSMeO

HO


28

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

21

10

OTBDMSMeO

BnO


0.600.60 0.800.80 1.001.00 1.201.20 1.401.40 1.601.60

OTBDMSMeO

BnO


29

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

44

10

21 24

46

29

10 10

90

41

OTBDMSMeO

BnO


-10-1000101020203030404050506060707080809090100100110110120120130130

OTBDMSMeO

BnO


30

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

OHMeO

BnO


707080809090100100110110120120130130140140150150160160

OHMeO

BnO


31

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

5.1

1.0

2.1 2.2

4.3 4.0

1.0 0.8

OHMeO

BnO


50506060707080809090100100110110120120130130140140

OHMeO

BnO

Compound (13’) 13C NMR 75 MHz, CDCl3.

32

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

48

20

44

20 19

81

09

BnOO

MeO


50506060707080809090100100110110120120130130140140

BnOO

MeO


33

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

2

21

40

20 20

81

10

BnOO

MeO


50506060707080809090100100110110120120130130140140

BnOO

MeO


34

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

0

OMeO

OO

BnO


3030404050506060707080809090100100110110120120130130140140

OMeO

OO

BnO


35

Compound (15) NOESY

36

0.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

20

39

OMeO

OO

BnO


3030404050506060707080809090100100110110120120130130140140

OMeO

OO

BnO


37

Compound (16) NOESY

38

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

32

1020 22

OMeO

OO

BnO


3030404050506060707080809090100100110110120120130130

OMeO

OO

BnO


39

Compound (17) NOESY

40

0.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

10 10 10 10 10

OMeO

OO

BnO


3030404050506060707080809090100100110110120120130130140140

OMeO

OO

BnO


41

Compound (18) NOESY

42

00112233445566778899

0

63

09

1824

3

07

BnOH

MeOO


50506060707080809090100100110110120120130130140140150150160160170170180180190190200200

BnOH

MeOO


43

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.58.08.08.58.59.09.09.59.5

CHOMeO

BnO


50506060707080809090100100110110120120130130140140150150160160170170180180190190200200

CHOMeO

BnO

Compound (19’) 13C NMR 75 MHz, CDCl3.

44

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

BnO

MeOOH


20203030404050506060707080809090100100110110120120130130140140

BnO

MeOOH


45

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

BnO

MeOOH


20203030404050506060707080809090100100110110120120130130140140

BnO

MeOOH


46

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

BnO

MeOOH


20203030404050506060707080809090100100110110120120130130

BnO

MeOOH


47

Compound (21) NOESY

48

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

BnO

MeOOH


3030404050506060707080809090100100110110120120130130140140

BnO

MeOOH


49

Compound (22) NOESY

50

b) Compounds generated by using (R)-phenylethylene glycol

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

6

26

1018 14 10 08

30

OH

O O


6060707080809090100100110110120120130130

OH

O O


51

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

6

09

216

23

091016

28 30

O

OOO

O


20203030404050506060707080809090100100110110120120130130140140150150160160170170180180190190200200

OPh

OOMeO

O


52

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

68

10

27

0

30

111014

21

O

O OON2


50506060707080809090100100110110120120130130140140

OPh

OOMeON2


53

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

38

11

22

10

40

0009

13

O

O

OMeO


50506060707080809090100100110110120120130130

O

O

Ph

O

OMe


54

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

57

1122

4033

07 10

O

O

OMeO


50506060707080809090100100110110120120130130140140

O

O

Ph

O

OMe


55

c) Cyclopropanation

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

OPh

OHPh


707080809090100100110110120120130130140140150150

OPh

OHPh


56

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

OPh

OPh

O

O


00252550507575100100125125150150175175200200

OPh

OPh

O O


57

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.58.08.0

OPh

OPh CHN2

O


404050506060707080809090100100110110120120130130140140150150

OPh

OPh CHN2

O


58

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

O

OPh

Ph

O

Compound(10)1H NMR 300 MHz, CDCl3.


59

Compound (10) NOESY

60

3) SPCTRAL DATA a) Compounds generated by using (1S, 2S)-1, 2-diphenylethane-1, 2-diol

O

OPh

Ph

O

O

6a” Whit solid, M.P 115 oC; [α]D

24 +60.7 (c 0.008, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.25-7.14 (m, 6H), 7.08-7.04 (m, 2H), 6.95-6.92 (m, 2H), 6.13 (ddd, J1 = 17.0 Hz, J2 = 11.0 Hz, J3 = 8.7 Hz, 1H), 5.94 (d, J = 9.3 Hz,1H) 5.28 (m, 1H), 5.26 (m, 1H), 4.38 (d, J = 9.2 Hz, 1H), 4.22 (dd, J1= 11.4 Hz, J2= 5.8 Hz, 1H), 4.16 (d, J = 5.7 Hz, 1H), 3.93 (dd, J1= 11.4 Hz, J2= 1.6 Hz, 1H), 3.52 (s, 3H), 3.26 (m, 1H); 13C NMR (75 MHz): δ 174.1, 137.0, 135.2, 133.7, 128.6, 128.3, 128.0, 127.6, 127.3, 118.4, 58.4, 50.2.

O

OPh

Ph

O

OMe

7a” [α]D

24 -138.9 (c 0.004, CHCl3); 1H NMR (500 MHz, CDCl3): δ 7.25-7.21 (m, 3H), 7.18-7.16 (m, 3H), 7.10-7.07 (m, 2H), 6.95-6.92 (m, 2H), 6.02 (d ,J = 9.2 Hz, 1H), 5.82 (ddd , J1 = 17.4 Hz, J2= 10.4 Hz , J3= 8.4 Hz, 1H) 5.22 (td, J1 = 17.3 Hz, J2 = 1.4 Hz, 1H), 5.18 (td, J1 = 10.4 Hz , J2 = 1.4 Hz, 1H), 4.35 (d, J= 9.2 Hz, 1H), 4.16 (t, J = 10.6 Hz , 1H), 4.05 (dd, J1 = 10.7 Hz, J2= 3.0 Hz, 1H), 4.02 (d, J = 3.16 Hz, 1H), 3.48 (s , 3H), 3.15 (m, 1H); 13C NMR (50MHz): δ 175.4, 137.2, 135.4, 134.1, 129.1, 128.1, 127.4, 117.8, 91.7, 86.7, 81.7, 73.6, 58.3, 52.5.

O

BnO

MeO

OO

15” [α]D

24 -15.0 (c 0.001, CHCl3); 1H NMR (500 MHz CDCl3): δ 7.29-7.21 (m, 5H), 4.58 (dd, J1= 6.66 Hz, J2 = 9.7 Hz, 1H), 4.55 (s, 2H), 4.24 (ddd, J1= 6.7 Hz, J2= 10.5 Hz, J3 = 4.1 Hz, 1H), 4.05 (dd, J1 = 11.4 Hz, J2 = 2.9 Hz, 1H), 3.90 (dd, J1 = 8.5 Hz, J2 = 2.4 Hz, 1H), 3.84 (dd, J1= 12.2 Hz, J2 = 4.1 Hz, 1H), 3.70 (dd, J1 = 2.0 Hz, J2 = 8.5 Hz, 1H), 3.38 (s, 3H), 3.34 (dd, J1 = 12.2 Hz, J2 = 10.5 Hz, 1H), 3.24 (m, 1H), 3.21 (m, 1H), 1.96

OO

H

H H HH

H

PhPh

O

OMeH

H

H

e

f

d c

a

h

ib

g

OO

H

H

O

H

H

H H

Ph

Ph H

H

H

OMe

e

f

dc b

a

h

i

g

O

O O

CH3CH3

H

H

H

H

HHH

HMeO

OH

H HH

Ph

f g1

g ba1

ac

e1

e d

61

(m, 1H),1.39 (s, 3H), 1.35 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 138.6, 128.2, 127.4, 127.4, 107.8, 96.0, 76.0, 76.0, 75.0, 74.2, 73.0, 69.6, 67.0, 59.0, 46.6, 27.5, 24.7.

17” [α]D

24 -6.2 (c 0.004, CHCl3); 1H NMR (500 MHz,CDCl3): δ 7.36-7.29 (m, 5H), 4.59 (dd, J1= 6.7 Hz, J2 = 9.7 Hz, 1H), 4.55 (s, 2H), 4.24 (ddd, J1 = 6.7 Hz, J2 = 10.5 Hz, J3 = 4.1 Hz, 1H), 4.06 (dd, J1 = 11.2 Hz, J2 = 2.8 Hz, 1H), 3.90 (dd, J1 = 8.4 Hz, J2 = 2.5 Hz, 1H), 3.85 (dd, J1 = 12.2 Hz, J2 = 4.06 Hz, 1H), 3.70 (dd, J1 = 1.9 Hz, J2 = 8.4 Hz, 1H), 3.38 (s,3H), 3.34 (dd, J1 = 12.2 Hz, J2 = 10.5 Hz, 1H), 3.24, (m, 1H), 3.21 (m, 1H), 1.96 (m, 1H),1.40(s, 3H) ,1.35 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 138.8, 127.4, 107.9, 76.2, 74.3, 7.12, 7.72, 7.14, 59.0, 46.7, 27.5, 24.8.

O

BnO

MeO

OO

O

O O

CH3CH3

H H

H

O

H H

H

H

H

Ph

MeO

H

H

HH

d

c b

a

a1g

g1

e1

e

f

62

4) 1H, 13C and NOESY NMR SPECTRA

0.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.0

O

O

O

Ph

O

Ph

Compound (6a”) 1H NMR 500 MHz, CDCl3.

6060707080809090100100110110120120130130140140150150160160170170

O

O

O

Ph

O

Ph


63

Compound (6a”) NOESY

64

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.5

10 10

O

OPh

PhO

OMe


50506060707080809090100100110110120120130130140140150150160160170170

O

OPh

PhO

OMe


65

Compound (7a”) NOESY

66

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5

O

BnO

MeO

OO

Compound (15”) 1H NMR 600 MHz, CDCl3.

Compound (15”) 13C NMR 150 MHz, CDCl3.

67

Compound (15”) NOESY

68

Compound(17”) 1H NMR 600 MHz, CDCl3.

Compound(17”) 13H NMR 150 MHz, CDCl3.

69

Compound (17”) NOESY

70

5) Chiral HPLC Analysis HPLC Analysis of Racemic 6a Conditions: λ=210 nm, mobile phase: 95:5 (nHex:IPA), Flow:1mL/min

71

HPLC Analysis of 6a Conditions: λ=210 nm, mobile phase: 95:5 (nHex:IPA), Flow:1mL/min

72

HPLC Analysis of 6a” Conditions: λ=210 nm, mobile phase: 95:5 (nHex:IPA), Flow:1mL/min

73

HPLC Analysis of Racemic 7a Conditions: λ=210 nm, mobile phase: 99:1 (nHex:IPA), Flow:0.7mL/min

74

HPLC Analysis of 7a Conditions: λ=210 nm, mobile phase: 99:1 (nHex:IPA), Flow:0.7mL/min

75

HPLC Analysis of 7a” Conditions: λ=210 nm, mobile phase: 99:1 (nHex:IPA), Flow:0.7mL/min

76

HPLC Analysis of racemic 2 Conditions: λ=210 nm, mobile phase: 98:2 (nHex:IPA), Flow:1mL/min

77

HPLC Analysis of 2 Conditions: λ=210 nm, mobile phase: 98:2 (nHex:IPA), Flow:1mL/min

78

HPLC Analysis of Racemic 3 Conditions: λ=210 nm, mobile phase: 98:2 (nHex:IPA), Flow:1mL/min

79

HPLC Analysis of 3 Conditions: λ=210 nm, mobile phase: 98:2 (nHex:IPA), Flow:1mL/min

80

HPLC Analysis of Racemic 10 Conditions: λ=254 nm, mobile phase: 95:5 (nHex:Ethanol), Flow:1mL/min

81

HPLC Analysis of 10 Conditions: λ=254 nm, mobile phase: 95:5 (nHex:Ethanol), Flow:1mL/min

82

6) X-ray Crystallographic analysis of 10 Crystal data for 10 C19H18O3 M = 294.33, orthorhombic, space group P212121, a = 10.1848(8) Å, b = 17.5488(14) Å, c = 8.8167(7) Å, V = 1575.8(2) Å3, ρcalc = 1.241 g m-3, λ= 0.71073Å, µ(Mo Kα ) = 0.083 mm-1, F000 = 624, T = 294(2) K. Total number of measured reflections is 15193. Rint = 0.0185. Final refinement to convergence on F2 gave R= 0.0329 (1541 obs. data only) and Rw = 0.0932 (1616 unique data), GOF = 1.042. CCDC reference number 690682.

highly enantioselective carbon-carbon bond …supporting information page no 1) experimental...

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