ja306062c si 002-bzoxozale
TRANSCRIPT
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
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Supporting Information
Decarbonylative CH Coupling of Azoles and Aryl Esters:
Unprecedented Nickel Catalysis and Application to the Synthesis
of Muscoride A
Kazuma Amaike, Kei Muto, Junichiro Yamaguchi,* and Kenichiro Itami*
Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan
E-mail: [email protected], [email protected]
Table of Contents
1. General S2
2. Preparation of Phenyl Esters S3S6
3. Nickel-catalyzed Decarbonylative CH Coupling S6S104. 13C-labeling Experiment S11
5. Preparation of Ni(dcype)(CO)2 Complex (4) S11
6. X-ray Crystal Structure Analysis of4 S12S13
7. Effect of Parameters S14S15
8. Alternative Protocols for Decarbonylative CH Coupling S15S16
9. Formal Synthesis of Muscoride A S17S19
10. 1H and 13C NMR Spectra S20S65
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1. General
Unless otherwise noted, all materials including dry solvents were obtained from commercial
suppliers and used as received. Ni(cod)2 and K3PO4 were obtained from Wako Chemicals.
1,2-Bis(dicyclohexylphosphino)ethane (dcype) was obtained from Sigma-Aldrich. 1,4-Dioxane was
freshly distilled by calcium hydride before coupling reaction. 5-Phenyloxazole (1B)[ 1 ],
5-phenylthiazole (1C)[ 2 ] and 2-phenylthiazole-4-carboxylate[ 3 ] were synthesized according to
procedures reported in the literature. Unless otherwise noted, all reactions were performed with dry
solvents under an atmosphere of argon in flame-dried glassware using standard vacuum-line
techniques. All CH bond arylation reactions were performed in 20-mL glass vessel tubes equipped
with J. Young O-ring tap and heated in an 8-well reaction block (heater + magnetic stirrer) unless
otherwise noted. All work-up and purification procedures were carried out with reagent-grade solvents
in air.
Analytical thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254
precoated plates (0.25 mm). The developed chromatogram was analyzed by UV lamp (254 nm). Flash
column chromatography was performed with E. Merck silica gel 60 (230400 mesh). Preparative
thin-layer chromatography (PTLC) was performed using Wakogel B5-F silica coated plates (0.75 mm)
prepared in our laboratory. High-resolution mass spectra (HRMS) were obtained from a JMS-T100TD
instrument (DART). Optical rotations were measured using a JASCO P-1010-GT digital polarimeter
with CHCl3 as the solvent. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL
JNM-ECA-600 (1H 600 MHz, 13C 150 MHz) spectrometer and a JEOL JNM-ECA-400 (1H 400 MHz,13C 100 MHz) spectrometer. Chemical shifts for1H NMR are expressed in parts per million (ppm)
relative to tetramethylsilane ( 0.00 ppm) or residual peak of benzene ( 7.16 ppm) or DMSO ( 2.50
ppm). Chemical shifts for13C NMR are expressed in ppm relative to CDCl3 ( 77.0 ppm), C6D6 (
128.06 ppm) or DMSO-d6 ( 39.52 ppm). Data are reported as follows: chemical shift, multiplicity (s
= singlet, d = doublet, dd = doublet of doublets, t = triplet, q = quartet, m = multiplet, br = broad
signal), coupling constant (Hz), and integration.
[1] Besselivre, F.; Mahuteau-Betzer, F.; Grierson, D. S.; Piguel, S.J. Org. Chem. 2008, 73, 3278.[2] Parisien, M.; Valette, D.; Fagnou, K.J. Org. Chem.2005, 70, 7578.[3] Chen, H.; O'Connor, S.; Cane, D. E.; Walsh, C. T. Chem. Biol.2001, 8, 899.
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2. Preparation of Phenyl Esters
Representative procedure: Phenyl nicotinate (2f)[4]
HO
O
N PhO
O
N
SOCl2, reflux 1h
;then NEt3, PhOH
DMAP, CH2Cl2RT, 1 h
[96%]
2f
Thionyl chloride (9 mL) was added to nicotinic acid (1.23 g, 10 mmol, 1.0 equiv) and the mixture was
stirred at reflux for 1 h. The solution was concentrated under vacuum. To a solution of the residue in
THF (10 mL) was added triethylamine (1.7 mL, 12 mmol, 1.2 equiv). After cooling the mixture to
0 C, phenol (941 mg, 10 mmol, 1.0 equiv) and a piece of 4,4-dimethylaminopyridine (DMAP) was
added and then the reaction mixture was warmed to room temperature. After stirring the mixture for 1
h, the resulting mixture was passed through a short silica gel pad with EtOAc. The filtrate was
concentrated under reduced pressure and the residue was purified by recrystallization from hexane to
afford 2fas a white solid (1.91 g, 96% yield). 1H NMR (400 MHz, CDCl3): 9.41 (d,J= 1.2 Hz, 1H),
8.86 (dd, J = 5.0, 1.8 Hz, 1H), 8.478.44 (m, 1H), 7.497.43 (m, 3H), 7.30 (t,J = 7.8 Hz, 1H),
7.267.22 (m, 2H); 13C NMR (100 MHz, CDCl3): 164.0, 154.2, 151.6, 150.7, 137.7, 129.8, 126.4,
125.8, 123.6, 121.7.
S
O
PhO
2b
Phenyl thiophene-2-carboxylate (2b)[5]
: Purification by recrystallization from hexane afforded 2b as
a white solid (96% yield). 1H NMR (400 MHz, CDCl3): 7.98 (dd,J= 4.0, 1.2 Hz, 1H), 7.66 (dd,J=
5.2, 1.2 Hz, 1H), 7.457.39 (m, 2H), 7.297.21 (m, 3H), 7.17 (dd,J= 5.2, 4.2 Hz, 1H); 13C NMR (100
MHz, CDCl3): 160.7, 150.7, 134.8, 133.6, 133.1, 129.6, 128.2, 126.1, 121.8.
S
O
PhO
2c
Phenyl thiophene-3-carboxylate (2c)[6]
: Purification by recrystallization from hexane afforded 2c as
a white solid (61% yield). 1H NMR (400 MHz, CDCl3): 8.31 (dd,J= 2.8, 1.2 Hz, 1H), 7.67 (dd,J=
[4] Yang, T.; Chan, N. Y.-K.; Sauve, A. A. J. Med. Chem.2007, 50, 6458.[5] Watson, D. A.; Fan, X.; Buchwald, S. L. J. Org. Chem.2008, 73, 7096.[6] Ren, W.; Emi, A.; Yamane, M. Synthesis2011, 2303.
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5.0, 1.4 Hz, 1H), 7.447.40 (m, 2H), 7.38 (dd,J= 5.0, 3.0 Hz, 1H), 7.297.25 (m, 1H), 7.217.19 (m,
2H); 13C NMR (100 MHz, CDCl3): 161.2, 150.8, 134.2, 133.1, 129.6, 128.4, 126.5, 126.0, 121.8.
O
O
PhO
2d
Phenyl furan-2-carboxylate (2d)[7]
: Purification by recrystallization from hexane afforded 2d as a
white solid (42% yield). 1H NMR (400 MHz, CDCl3): 7.68 (m, 1H), 7.457.38 (m, 3H), 7.297.21
(m, 3H), 6.60 (dd,J= 3.4, 1.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): 157.1, 150.3, 147.3, 144.2,
129.7, 126.2, 121.7, 119.6, 112.3.
O
O
PhO
2e
Phenyl furan-3-carboxylate (2e): Purification by recrystallization from hexane afforded 2e as a
white solid (59% yield). 1H NMR (400 MHz, CDCl3): 8.19 (dd,J= 1.4, 0.6 Hz, 1H), 7.50 (t,J= 1.6
Hz, 1H), 7.447.39 (m, 2H), 7.287.24 (m, 1H), 7.197.16 (m, 2H), 6.87 (dd,J= 2.0, 0.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3): 161.6, 150.6, 148.8, 144.2, 129.6, 126.1, 121.8, 119.0, 110.2; HRMS
(DART) m/zcalcd for C11H9O3 [MH]+: 189.05517, found 189.05517.
N
O
PhO
2g
Phenyl isonicotinate (2g): Purification by recrystallization from hexane afforded 2g as a white solid
(99% yield). 1H NMR (400 MHz, CDCl3): 8.87 (d,J= 6.0 Hz, 2H), 8.01 (d,J= 6.4 Hz, 2H), 7.46 (t,
J= 8.2 Hz, 2H), 7.337.22 (m, 3H); 13C NMR (100 MHz, CDCl3): 163.9, 151.0, 150.6, 137.0, 129.8,
126.5, 123.4, 121.5; HRMS (DART) m/zcalcd for C12H10NO2 [MH]+: 200.07115, found 200.07108.
N
O
PhO
2h
Phenyl picolinate (2h): Purification by recrystallization from hexane afforded 2h as a white solid
(99% yield). 1H NMR (400 MHz, CDCl3): 8.868.84 (m, 1H), 8.28 (d,J= 8.0 Hz, 1H), 7.92 (td,J=
8.0, 2.0 Hz, 1H), 7.577.54 (m, 1H), 7.487.41 (m, 2H), 7.317.25 (m, 3H);13C NMR (100 MHz,
[7] Zhang, L.; Zhang, G.; Zhang, M.; Cheng, J.J. Org. Chem.2010, 75, 7472.
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CDCl3): 164.0, 151.0, 150.3, 147.7, 137.4, 129.7, 127.5, 126.3, 126.0, 121.8; HRMS (DART)m/z
calcd for C12H10NO2 [MH]+: 200.07115, found 200.07113.
N
NO
PhO
2i
Phenyl pyrazine-2-carboxylate (2i): Purification by flash column chromatography (hexane/EtOAc =
3:1) afforded 2i as a white solid (51% yield). 1H NMR (400 MHz, CDCl3): 9.48 (s, 1H), 8.85 (d,J=
1.2 Hz, 1H), 8.82 (d,J= 1.2 Hz, 1H), 7.46 (t,J= 7.8 Hz, 2H), 7.397.21 (m, 3H); 13C NMR (100
MHz, CDCl3): 162.7, 150.6, 148.3, 146.9, 144.8, 143.1, 129.8, 126.6, 121.6; HRMS (DART)m/z
calcd for C11H9N2O2 [MH]+: 201.06640, found 201.06621
N
O
PhO
Ph
2j
Phenyl 2-phenylquinoline-4-carboxylate (2j): Purification by flash column chromatography
(hexane/EtOAc = 10:1) afforded 2j as a white solid (43% yield). 1H NMR (400 MHz, CDCl3): 8.86
(d,J= 8.8 Hz, 1H), 8.65 (s, 1H), 8.298.24 (m, 3H), 7.80 (dd,J= 8.4, 6.8 Hz, 1H), 7.65 (dd,J= 8.6,7.0 Hz, 1H), 7.56 (t,J= 7.8 Hz, 2H), 7.50 (t,J= 7.6 Hz, 3H), 7.367.32 (m, 3H); 13C NMR (100 MHz,
CDCl3): 164.9, 156.9, 150.7, 149.5, 138.8, 134.8, 130.6, 130.2, 130.0, 129.9, 129.1, 128.3, 127.6,
126.6, 125.4, 124.2, 121.8, 121.0; HRMS (DART) m/zcalcd for C22H16NO2 [MH]+: 326.11810, found
326.11815.
S
N
O
PhO
Ph2k
Phenyl 2-phenylthiazole-4-carboxylate (2k): Purification by flash column chromatography
(hexane/EtOAc = 5:1) afforded 2kas a white solid (73% yield). 1H NMR (400 MHz, CDCl3): 8.35 (s,
1H), 8.068.03 (m, 2H), 7.487.41 (m, 5H), 7.307.25 (m, 3H);13C NMR (100 MHz, CDCl3): 169.3,
159.9, 150.7, 147.2, 132.8, 131.0, 129.6, 129.2, 128.8, 127.1, 126.2, 121.8; HRMS (DART)m/zcalcd
for C16H12NO2S[MH]+: 282.05887, found 282.05868.
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PhO
O
2l
Phenyl naphthalene-2-carboxylate (2l)[8]
: Purification by recrystallization from hexane afforded 2l
as a white solid (99% yield). 1H NMR (400 MHz, CDCl3): 8.81 (d,J= 0.8 Hz, 1H), 8.21 (dd,J= 8.8,
1.6 Hz, 1H), 8.02 (dd,J= 8.0, 0.8 Hz, 1H), 7.987.91 (m, 2H), 7.677.56 (m, 2H), 7.507.44 (m, 2H),
7.337.27 (m, 3H); 13C NMR (100 MHz, CDCl3): 165.5, 151.2, 136.0, 132.7, 132.1, 129.7, 129.6,
128.8, 128.5, 128.0, 127.0, 126.9, 126.1, 125.6, 121.9.
O
13C
N
H
1A-13C
[2-13
C]Benzoxazole (1A-13C 99% purity): A mixture of triethyl orthoformate (formyl-13C, 99% purity,
500 mg, 3.4 mmol, 1.0 equiv) and 2-aminophenol (742 mg, 6.8 mmol, 2.0 equiv) was refluxed in
toluene (1.2 mL) for 2 h. After cooling the mixture to room temperature, the mixture was concentrated
and the residue was purified by flash column chromatography (hexane/EtOAc = 10:1) to afford
1A-13C(295.0 mg, 72%) as colorless oil. 1H NMR (400 MHz, CDCl3): 8.11 (d,1JCH = 232.4 Hz, 1H),
7.817.78 (m, 1H), 7.617.58 (m, 1H), 7.437.35 (m, 2H); 13C NMR (100 MHz, CDCl3): 152.6,
150.1 (JCC = 3.8 Hz), 140.2 (JCC = 2.9 Hz), 125.7, 124.7, 120.8 (JCC = 6.7 Hz), 111.1 (JCC = 3.8 Hz);
HRMS (DART) m/zcalcd for C613CH6NO[MH]
+: 121.04829, found 121.04836.
3. Nickel-catalyzed Decarbonylative CH Coupling
Ni(cod)2 (10 mol%)dcype (20 mol%)K3PO4 (2.0 equiv)
1,4-dioxane150 C, 24 h
Z
N
H PhO+
O
Z
N
Ar
Ar
1A1C (1.0 equiv) 2b2k (1.5 equiv) 3
Z = O, S
General Procedure:A 20-mL glass vessel equipped with J. Young O-ring tap containing a magnetic
stirring bar and K3PO4 (170.0 mg, 0.80 mmol, 2.0 equiv) was dried with a heatgun under reduced
pressure and filled with N2 after cooling to room temperature. To this vessel was added a phenyl ester
derivative 2 (0.60 mmol, 1.5 equiv), then introduced into an argon-atmosphere glovebox. To the
[8] Rosa, J. N.; Reddy, R. S.; Candeias, N, R.; Cal, P. M. S. D.; Gois, P. M. P. Org. Lett.2010, 12, 2686.
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reaction vessel were added Ni(cod)2 (11.2 mg, 0.04 mmol, 10 mol%) and
1,2-bis(dicyclohexylphosphino)ethane (dcype: 33.8 mg, 0.08 mmol, 20 mol%). The vessel was taken
out of the glovebox, then to it was added an azole1 (0.40 mmol) and dry 1,4-dioxane (1.5 mL) under a
stream of N2. The vessel was sealed with O-ring tap and then heated at 150 C for 24 h in an 8-well
reaction block with stirring. After cooling the reaction mixture to room temperature, the mixture was
passed through a short silica gel pad with EtOAc. The filtrate was concentrated and the residue was
subjected to preparative thin-layer chromatography to afford a decarbonylative coupling product
(2-arylated azole 3).
N
O S
3Ab: 96%
2-(Thiophen-2-yl)benzoxazole (3Ab)
[ 9 ]: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 10:1) afforded 3Ab (77.3 mg, 96%) as a white solid. 1H NMR (400 MHz, CDCl3):
7.89 (dd,J= 3.8, 1.4 Hz, 1H), 7.767.70 (m, 1H), 7.567.50 (m, 2H), 7.367.29 (m, 2H), 7.16 (dd,J=
5.0, 3.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): 159.1, 150.5, 142.1, 130.3, 130.0, 129.7, 128.3,
125.2, 124.8, 119.9, 110.5; HRMS (DART) m/z calcd for C11H8NOS [MH]+: 202.03266, found
202.03279.
N
OS
3Ac: 96%
2-(Thiophen-3-yl)benzoxazole (3Ac)[9]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 10:1) afforded 3Ac (77.2 mg, 96%) as a white solid. 1H NMR (400 MHz, CDCl3):
8.19 (dd,J= 2.6, 1.0 Hz, 1H), 7.79 (dd,J= 5.0, 1.0 Hz, 1H), 7.777.71 (m, 1H), 7.587.50 (m, 1H),
7.487.42 (m, 1H), 7.387.32 (m, 2H);13C NMR (100 MHz, CDCl3): 159.8, 150.4, 142.0, 129.4,
128.2, 127.1, 126.7, 125.1, 124.7, 120.0, 110.6; HRMS (DART) m/z calcd for C11H8NOS [MH]+:
202.03266, found 202.03249.
N
O O
3Ad: 86%
[9] Derridj, F.; Djebbar, S.; Benali-Baitich, O.; Doucet, H.J. Organomet. Chem.2008, 693, 135.
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2-(Furan-2-yl)benzoxazole (3Ad)[ 10 ]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 10:1) afforded 3Ad (63.7 mg, 86%) as a white solid.1H NMR (400 MHz, CDCl3):
7.827.73 (m, 1H), 7.727.65 (m, 1H), 7.627.55 (m, 1H), 7.437.34 (m, 2H), 7.28 (d,J= 3.6 Hz,
1H), 6.62 (dd,J= 3.6, 2.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): 155.4, 150.2, 145.8, 142.7, 141.7,
125.4, 124.9, 120.2, 114.4, 112.4, 110.7; HRMS (DART) m/zcalcd for C11H8NO2 [MH]+: 186.05550,
found 186.05563.
N
OO
3Ae: 86%
2-(Furan-3-yl)benzoxazole (3Ae)[ 11 ]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 10:1) afforded 3Ae (63.8 mg, 86%) as a white solid.1
H NMR (400 MHz, CDCl3): 8.22 (d,J= 0.8 Hz, 1H), 7.747.68 (m, 1H), 7.567.48 (m, 2H), 7.357.28 (m, 2H), 7.03 (d,J= 1.6
Hz, 1H); 13C NMR (100 MHz, CDCl3): 158.4, 150.3, 144.5, 144.4, 141.9, 125.0, 124.6, 119.8, 115.5,
110.5, 109.0; HRMS (DART) m/zcalcd for C11H8NO2 [MH]+: 186.05550, found 186.05544.
N
N
O
3Af: 70%
2-(Pyridin-3-yl)benzoxazole (3Af)[ 12 ]: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Af(54.9 mg, 70%) as a white solid. 1H NMR (400 MHz, CDCl3):
9.45 (d, J = 1.6 Hz, 1H), 8.74 (dd, J = 5.0, 1.4 Hz 1H), 8.518.45 (m, 1H), 7.837.72 (m, 1H),
7.617.55 (m, 1H), 7.47 (dd,J= 8.2, 5.0 Hz, 1H), 7.407.34 (m, 2H);13C NMR (100 MHz, CDCl3):
160.8, 152.2, 150.9, 148.9, 141.9, 134.8, 125.8, 125.0, 123.8, 123.6, 120.4, 110.9; HRMS (DART)m/z
calcd for C12H9N2O[MH]+: 197.07149, found 197.07148.
N
N
O
3Ag: 92%
2-(Pyridin-4-yl)benzoxazole (3Ag)[9]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Ag (72.6 mg, 92%) as a white solid.1H NMR (400 MHz, CDCl3):
8.81 (dd,J= 4.4, 1.6 Hz, 2H), 8.06 (dd,J= 4.6, 1.8 Hz, 2H), 7.877.78 (m, 1H), 7.657.58 (m, 1H),
[10] Guru, M. M.; Ali, M. A.; Punniyamurthy, T.J. Org. Chem.2011, 76, 5295.[11] Barbero, N.; Carril, M.; SanMartin, R.; Domnguez, E. Tetrahedron2007, 63, 10425.[12] Derridj, F.; Roger, J.; Geneste, F.; Djebbar, S.; Doucet, H.J. Organomet. Chem.2009, 694, 455.
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7.487.38 (m, 2H); 13C NMR (100 MHz, CDCl3): 160.6, 150.9, 150.8, 141.8, 134.3, 126.4, 125.2,
121.0, 120.7, 111.0; HRMS (DART) m/zcalcd for C12H9N2O[MH]+: 197.07149, found 197.07132.
N
N
O
3Ah: 57%
2-(Pyridin-2-yl)benzoxazole (3Ah)[12]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Ah (44.5 mg, 57%) as a white solid.1H NMR (400 MHz, CDCl3):
8.82 (d, J = 4.4 Hz, 1H), 8.36 (d,J = 8.0 Hz, 1H), 7.957.80 (m, 2H), 7.67 (d,J = 7.2 Hz, 1H),
7.607.35 (m, 3H); 13C NMR (100 MHz, CDCl3): 161.5, 151.1, 150.4, 146.2, 141.9, 137.2, 126.1,
125.6, 125.0, 123.5, 120.7, 111.3; HRMS (DART) m/zcalcd for C12H9N2O[MH]+: 197.07149, found
197.07148.
N
NN
O
3Ai: 52%
2-(Pyrazin-2-yl)benzoxazole (3Ai): Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Ai (41.4 mg, 52%) as a white solid. 1H NMR (400 MHz, CDCl3):
9.58 (d,J= 1.2 Hz, 1H), 8.828.68 (m, 2H), 7.86 (dd,J= 6.6, 2.2 Hz, 1H), 7.68 (dd,J= 7.0, 1.8 Hz,
1H), 7.487.38 (m, 2H); 13C NMR (100 MHz, CDCl3): 159.4, 151.0, 146.2, 144.71, 144.65, 142.0,
141.6, 126.7, 125.3, 121.0, 111.3; HRMS (DART) m/zcalcd for C11H8N3O[MH]+: 198.06674, found
198.06687.
N
N
O
Ph
3Aj: 85%
2-(2-Phenylquinolin-4-yl)benzoxazole (3Aj): Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Aj (109.8 mg, 85%) as a white solid. 1H NMR (400 MHz, CDCl3):
9.44 (d,J= 8.8 Hz, 1H), 8.73 (s, 1H), 8.28 (t,J= 7.2 Hz, 1H), 7.947.92 (m, 1H), 7.82 (t,J= 7.2 Hz,
1H), 7.747.70 (m, 2H), 7.58 (t,J= 7.6 Hz, 2H), 7.537.44 (m, 3H); 13C NMR (100 MHz, CDCl3):
161.0, 156.9, 150.4, 149.5, 142.2, 139.1, 131.9, 130.6, 130.2, 129.9, 129.1, 128.1, 127.7, 126.5, 126.3,
125.2, 123.7, 121.0, 119.6, 111.0; HRMS (DART) m/zcalcd for C22H15N2O[MH]+: 323.11844, found
323.11834.
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SN
O
3Ak: 74%
NPh
2-(2-Phenylthiazol-4-yl)benzoxazole (3Ak): Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Ak(82.0 mg, 74%) as a white solid. 1H NMR (400 MHz, CDCl3):
8.228.21 (m, 1H), 8.118.09 (m, 2H), 7.847.82 (m, 1H), 7.647.62 (m, 1H), 7.487.47 (m, 3H),
7.407.37 (m, 2H); 13C NMR (100 MHz, CDCl3): 170.0, 158.4, 150.6, 144.5, 141.9, 132.8, 130.9,
129.1, 127.2, 125.7, 125.0, 122.3, 120.6, 111.0; HRMS (DART) m/z calcd for C16H11N2OS[MH]+:
279.05921, found 279.05907.
N
N
OPh
3Bf: 96%
5-Phenyl-2-(pyridin-3-yl)oxazole (3Bf)[13]
: Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Bf(85.0 mg, 96%) as a white solid. 1H NMR (400 MHz, CDCl3):
9.35 (d, J = 1.2 Hz, 1H), 8.70 (dd, J = 5.0, 1.4 Hz, 1H), 8.408.32 (m, 1H), 7.787.70 (m, 2H),
7.517.35 (m, 5H); 13C NMR (100 MHz, CDCl3): 158.9, 152.2, 151.1, 147.7, 133.5, 129.2, 129.0,
127.7, 124.5, 123.8, 123.8, 123.7; HRMS (DART) m/zcalcd for C14H11N2O[MH]+: 223.08715, found
223.08715.
N
N
SPh
3Cf: 77%
5-Phenyl-2-(pyridin-3-yl)thiazole (3Cf): Purification by preparative thin-layer chromatography
(hexane/EtOAc = 5:1) afforded 3Cf(73.2 mg, 77%) as a white solid. 1H NMR (400 MHz, CDCl3):
9.18 (d, J = 1.6 Hz, 1H), 8.668.62 (m, 1H), 8.258.19 (m, 1H), 8.05 (s, 1H), 7.617.56 (m, 2H),
7.447.31 (m, 4H); 13C NMR (100 MHz, CDCl3): 163.5, 150.7, 147.6, 140.3, 139.5, 133.3, 130.9,
129.7, 129.2, 128.7, 126.8, 123.8; HRMS (DART) m/zcalcd for C14H11N2S[MH]+: 239.06429, found
239.06437.
[13] Santos, A.; Kam, L. E.; Grimaud, L.; Ronsseray, C. Chem. Commun. 2009, 3907.
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4.13
C-labeling Experiment
O
13C
N
H +
PhO
O
N O
13C
N
N
standard
conditions
[72%]
1A-13C
(99% purity)2f
(1.5 equiv)3Af-13C
(99% purity)
3-(2-[2-13
C]Benzoxazolyl)pyridine (3Af-13C): Following the general procedure with 1A-13C (0.4
mmol) and 2f (0.6 mmol, 1.5 equiv), the crude product was purified by preparative thin-layer
chromatography (hexane/EtOAc = 5:1) to afford 3Af-13C (57.7 mg, 72%) as a white solid. 1H NMR
(400 MHz, CDCl3): 9.49 (t, J = 1.8 Hz, 1H), 8.78 (dd,J = 4.8, 0.8 Hz, 1H), 8.558.49 (m, 1H),
7.887.84 (m, 1H), 7.657.59 (m, 1H), 7.48 (dd,J= 8.2, 5.0 Hz, 1H), 7.447.37 (m, 2H); 13C NMR
(100 MHz, CDCl3): 160.7, 152.1, 150.8 (JCC = 3.8 Hz), 148.9 (JCC = 2.8 Hz), 141.9 (JCC = 1.9 Hz),
134.8, 125.8, 125.0, 123.7 (JCC = 4.8 Hz), 123.4 (JCC = 52.2 Hz), 120.4 (JCC = 7.7 Hz), 110.8 (JCC =
3.9 Hz); HRMS (DART) m/zcalcd for C1113CH9N2O[MH]
+: 198.07484, found 198.07500.
5. Preparation of Ni(dcype)(CO)2 Complex (4)
Ni
PP
OC CO
Ni(dcype)(CO)2 (4)
Ni(dcype)(CO)2 (4): In an argon-atmosphere glovebox,Ni(CO)2(PPh3)2 (1.92 g, 3.0 mmol, 1.0 equiv)
and 1,2-bis(dicyclohexylphosphino)ethane (dcype: 1.39 g, 3.3 mmol, 1.1 equiv) were added to the
reaction vessel. The vessel was taken out of the glovebox, then to it was added THF (9 mL). The
mixture was stirred at 40 C for 2 h. After cooling the mixture to room temperature, the mixture was
concentrated and the residue was purified by recrystallization from THF and hexane to afford 4 (1.55
g, 96%) as a white solid. 1H NMR (400 MHz, C6D6): 1.95 (br, 2H), 1.92 (br, 2H), 1.721.59 (m,
20H), 1.361.13 (m, 24H); 13C NMR (100 MHz, C6D6): 205.0, 35.8 (t,JPC = 8.2 Hz), 29.3, 28.5,
27.6, 27.53, 27.47, 27.41, 26.7, 23.2 (t,JPC = 19.7 Hz);31P NMR (160 MHz, C6D6): 64.0; IR (KBr):
1979, 1922, 1912 cm-1; anal calcd for C28H50O2P2Ni: C 62.35, H 9.34, found C 62.47, H 8.97.
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6. X-ray Crystal Structure Analysis of 4
A suitable crystal of 4 was mounted with mineral oil on a glass fiber and transferred to the
goniometer of a Rigaku Saturn CCD diffractometer. Graphite-monochromated Mo K radiation (=
0.71070 ) was used. The structures were solved by direct methods with (SIR-97)[14] and refined by
full-matrix least-squares techniques against F2 (SHELXL-97).[15] The intensities were corrected for
Lorentz and polarization effects. The non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were placed using AFIX instructions. Details of the crystal data and a summary of the intensity
data collection parameters for4 are listed in Table S1.
Table S1. Crystallographic data and structure refinement details for4.
4
formula C63H104Ni2O4P4
fw 1165.75
T(K) 123(2)
() 0.71070
cryst syst Monoclinic
space group P21/n
a, () 10.497(3)
b, () 18.260(4)
c, () 17.011(4)
,(deg) 90
, (deg) 107.278(3),(deg) 90
V, (3) 3113.7(13)
Z 2
Dcalc, (g / cm3) 1.243
m (mm-1) 0.751
F(000) 1258
cryst size (mm) 0.15 0.10 0.01
2 range, (deg) 3.0225.00
reflns collected 20681
indep reflns/Rint 5466/0.0574
params 352
GOF onF2 1.138
R1, wR2 [I>2(I)] 0.0672, 0.1448
R1, wR2 (all data) 0.0810, 0.1539
abs struct param -0.1(2)
[14] Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G.G.; Polidori, G.; Spagna, R.J. Appl. Crystallogr. 1999, 32, 115.
[15] Sheldrick, G. M. University of Gttingen: Gttingen, Germany, 1997.
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Figure S1. ORTEP drawing of4 with 50% thermal ellipsoid. All hydrogen atoms are omitted for
clarity.
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S15
The reaction only worked when aryl esters were used (i.e. alkyl esters such as methyl esters, or
t-butyl esters did not work at all). The effect of the aryl-substituent of carboxylic acids is shown below
in Table S3. Although these results indicate that phenyl esters are not the best substrates for this
reaction (e.g., fluorophenyl esters give a higher yield), we used user-friendly phenyl esters in this
study.
Table S3. Effect of Parameters.
O
NH
O
ArO+
10 mol% Ni(cod)220 mol% dcype
2.0 equiv K3PO4
1,4-dioxane
150 C, 24 h1A (0.4 mmol) (1.5 equiv) 3Aa
O
N
MeMe
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
o-
m-
p-
: 76%
: 76%
: 68%
82%[a] 46% 25%
57%
OMe
81%
OMe
MeO
F
91% 86%
96% 35%
MeO
F3C
6% 39% 41%
O
H
O
MeON
H
O
Aryl substituents(GC yield)
[a] Isolated yields.
8. Alternative Protocols for Decarbonylative CH Coupling
Ni(dcype)(CO)2 (10 mol%)K3PO4 (2.0 equiv)
1,4-dioxane150 C, 24 h
O
NH +
O
N
1A (0.40 mmol) 2b (1.5 equiv) 3Ab
SPhO
O
S
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A 20-mL glass vessel equipped with J. Young O-ring tap containing a magnetic stirring bar and
K3PO4 (170.0 mg, 0.80 mmol, 2.0 equiv) was dried with a heatgun under reduced pressure and filled
with nitrogen after cooling to room temperature. To this vessel were added 2b(122.6 mg, 0.60 mmol,
1.5 equiv) and Ni(dcype)(CO)2 (4: 21.6 mg, 0.04 mmol, 10 mol%). Then, this vessel was vacuumed
and backfilled with nitrogen for three times. To this vessel were added 1A (47.6 mg, 0.40 mmol) and
dry 1,4-dioxane (1.5 mL) under a stream of nitrogen. The vessel was sealed with O-ring tap and then
heated at 150 C for 24 h in an 8-well reaction block with stirring. After cooling the reaction mixture
to room temperature, the mixture was passed through a short silica gel pad with EtOAc. The filtrate
was concentrated and the residue was subjected to preparative thin-layer chromatography
(hexane/EtOAc = 10:1) to afford 3Ab (77.3 mg, 96%).
NiCl2 (10 mol%)dcype (20 mol%)
Zn (2.0 equiv)K3PO4 (2.0 equiv)
1,4-dioxane150 C, 24 h
O
NH +
O
N
1A (0.40 mmol) 2b (1.5 equiv) 3Ab
SPhO
O
S
A 20-mL glass vessel equipped with J. Young O-ring tap containing a magnetic stirring bar and
K3PO4 (170.0 mg, 0.80 mmol, 2.0 equiv) was dried with a heatgun under reduced pressure and filled
with nitrogen after cooling to room temperature. To this vessel were added 2b(122.6 mg, 0.60 mmol,
1.5 equiv), NiCl2 (5.2 mg, 0.04 mmol, 10 mol%) and activated Zn (52.4 mg, 0.80 mmol, 2.0 equiv),
then introduced into an argon-atmosphere glovebox. To the reaction vessel was added
1,2-bis(dicyclohexylphosphino)ethane (dcype: 33.8 mg, 0.08 mmol, 20 mol%). The vessel was taken
out of the glovebox, then to it was added 1A (47.6 mg, 0.40 mmol) and dry 1,4-dioxane (1.5 mL)
under a stream of nitrogen. The vessel was sealed with O-ring tap and then heated at 150 C for 24 h
in an 8-well reaction block with stirring. After cooling the reaction mixture to room temperature, the
mixture was passed through a short silica gel pad with EtOAc. The filtrate was concentrated and the
residue was subjected to preparative thin-layer chromatography (hexane/EtOAc = 10:1) to afford 3Ab
(60.4 mg, 75%).
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9. Formal Synthesis of Muscoride A
Methyl ester11 was prepared according to reported procedure by Wipf[16].
O
N
BocN
O
MeO
Me
LiOHH2O
THF/H2O (1 : 1)O
N
BocN
O
HO
Me
O
N
BocN
O
PhO
Me
PhOH
EDCHClcat. DMAP
CH2Cl2
phenyl ester 8methyl ester 11 carboxylic acid 12[84%, 2 steps]
H H H
Phenyl ester 8: To a 100-mL round bottom flask containing methyl ester11 (2.17 g, 7.0 mmol)
were added THF (20 mL), (20 mL), and LiOHH2O (590.0 mg, 2.0 equiv). After stirring the mixture
for 1 h at room temperature, THF was removed under the vacuo. Under 0 C, pH of this residue was
adjusted to 2 by addition of 1 M HCl. The reaction mixture was then extracted with CH2Cl2 (3 30
mL), and the combined organic layer was dried over Na2SO4 and then filtrated. After concentrating
this mixture, oxazole carboxylic acid 12 was obtained. This product was used without further
purification.
To a 100-mL round bottom flask containing 12 were added phenol (0.724 g, 1.1 equiv),
1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCHCl: 1.48 g, 1.1 equiv),
N,N-dimethylaminopyridine (DMAP: 0.214 g, 0.25 equiv), and CH2Cl2 (60 mL). After stirring the
mixture for 9 h, this reaction mixture was quenched with saturated NaHCO3 aq. and extracted withCH2Cl2 (3 30 mL). The combined organic layer was dried over Na2SO4, and then filtrated.
Following evaporation of the solvent under reduced pressure, the residue was purified by flash column
chromatography (hexane/EtOAc = 3:1 to 2:1) to afford phenyl ester8 as colorless viscous oil (2.18 g,
84% over 2 steps). Rf 0.48 (hexane/EtOAc = 1:1);1H NMR (600 MHz, DMSO-d6, 373 K): 7.46 (t,J
= 7.6 Hz, 2H), 7.30 (t, J = 7.6 Hz, 1H), 7.23 (d,J = 7.6 Hz, 2H), 4.88 (dd,J = 7.6, 3.5 Hz, 1H),
3.523.41 (m, 2H), 2.64 (s, 3H), 2.372.26 (m, 1H), 2.101.97 (m, 2H), 1.961.88 (m, 1H), 1.35 (s,
9H); 13C NMR (150 MHz, DMSO-d6, 373 K): 162.6, 159.5, 156.3, 152.8, 149.8, 128.9, 126.0, 125.3,
121.1, 78.6, 53.7, 45.8, 30.9, 27.5, 22.8, 11.3; HRMS (DART) m/z calcd for C20H25N2O5 [MH]+:
373.17635, found 373.17613. []D20 = 62 (c = 1.0, CHCl3).
[16] Wipf, P.; Venkatraman, S.J. Org. Chem. 1996, 61, 6517.
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Me O
O
CN
O
OMe+
DBU
THF, 0 C -> r.t.
[93%]
O
N
Me
OMe
OHO
Me
7
Methyl-5-methyloxazole carboxylate (7)[17]: To a solution of methyl 2-isocyanoacetate (2.41 g, 25
mmol) in 25 mL of THF was added DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, 4.24 g, 1.1 equiv).
Cooling the reaction mixture to 0 C, the solution of acetic anhydride (2.81 g, 1.1 equiv) was added
slowly. Warming up to room temperature, the reaction mixture was stirred. The progress of the
reaction was monitored by TLC. On completion of reaction, the reaction mixture was concentrated in
vacuo. To this vessel was added 30 mL of EtOAc and 20 mL of water. The aqueous layer was
extracted with EtOAc (20 mL 3) and the combined organic layer was treated with Na2SO4 and thenfiltered. Following evaporation of the solvent under reduced pressure, the crude residue was purified
by flash column chromatography (hexane/EtOAc = 2:1) to afford 7 as a white solid (3.20 g, 93%
yield). Rf0.41 (hexane/EtOAc = 1:1);1H NMR (400 MHz, CDCl3): 7.75 (s, 1H), 3.92 (s 3H), 2.65 (s,
3H); 13C NMR (100 MHz, CDCl3): 162.5, 156.5, 148.8, 127.0, 51.9, 11.8.
Ni(cod)2 (20 mol%)
dcype (40 mol%)K3PO4 (2.0 equiv)
1,4-dioxane165 C, 2 h
[39%]
O
N
Me
HO
N
Me
PhO
O
NO
t-BuO
O
OMe
+
7 (1.5 equiv) 8 (1.0 equiv)
H
N
OMe
O
OMe
O
N
Me
N
t-BuO
O
9
H
Methyl ester 9: A 20-mL glass vessel equipped with J. Young O-ring tap containing a magnetic
stirring bar was dried with a heatgun under reduced pressure and filled with nitrogen after cooling to
room temperature. To this vessel was added the solution of phenyl ester8 (111.7 mg, 0.30 mmol) in
CH2Cl2. After the concentration under the vacuo, to this was added oxazole 7 (63.5 mg, 1.5 equiv),
then introduced inside an argon atmosphere glovebox. In the glovebox, to the vessel were added
Ni(cod)2 (16.5 mg, 0.06 mmol, 20 mol%), 1.2-bis(dicyclohexylphosphino)ethane (dcype: 50.7 mg,
0.12 mmol, 40 mol%) and K3PO4 (127.3 mg, 2.0 equiv). The vessel was taken out of the glovebox,
then to it was added 1,4-dioxane (1.2 mL) under a stream of nitrogen. The vessel was sealed with
O-ring tap and then heated at 165 C for 2 h in an 8-well reaction block with stirring. After cooling the
reaction mixture to room temperature, the mixture was passed through a short silica gel pad with
EtOAc. The filtrate was concentrated and the residue was subjected to preparative thin-layer
[17] Muto, K.; Yamaguchi, J.; Itami, K.J. Am. Chem. Soc. 2012, 134, 169.
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S19
chromatography (hexane/EtOAc = 3:2) to afford coupling product 9 (45.7 mg, 39%) as a colorless
viscous oil. Rf = 0.31 (hexane/EtOAc = 1:1);1H NMR (600 MHz, DMSO-d6, 373 K): 4.86 (dd,J=
7.2, 3.0 Hz, 1H), 3.85 (s, 3H), 3.533.40 (m, 2H), 2.64 (s, 3H), 2.61 (s, 3H), 2.352.26 (m, 1H),
2.081.97 (m, 2H), 1.961.88 (m, 1H), 1.32 (s, 9H); 13C NMR (150 MHz, DMSO-d6, 373 K):
163.3, 161.4, 155.0, 153.0, 152.7, 149.2, 127.3, 123.5, 78.5, 53.7, 50.8, 45.8, 30.9, 27.5, 22.8, 11.0,
10.5; HRMS (DART) m/zcalcd for C19H25N3O6 [MH]+: 392.18216, found 392.18213. []D
21= 53 (c =
1.1, CHCl3)
10
O
N
Me
N
O
N
Me
O
O
O
t-BuO
HMeMe
Prenyl ester 10: Prenyl ester10 was synthesized from 9 according to the synthetic method developed
by Wipf[14]. 10 was obtained as colorless viscous oil. Rf = 0.42 (hexane/EtOAc = 1:1). 1H NMR (600
MHz, d6-DMSO, 373 K): 5.43 (t,J= 6.9 Hz, 1H), 4.894.84 (m, 1H), 4.78 (d,J= 6.9 Hz, 2H), 3.45
(m, 2H), 2.63 (s, 3H), 2.61 (s, 3H), 2.352.26 (m, 1H), 2.081.96 (m, 2H), 1.951.88 (m, 1H), 1.77 (s,
3H), 1.75 (s, 3H), 1.32 (s, 9H); 13C NMR (150 MHz, d6-DMSO, 373 K):
162.3, 160.9, 155.0, 153.0, 152.7, 149.2, 138.0, 127.5, 123.6, 118.2, 78.5, 60.5, 53.7, 45.8, 31.0, 27.
5, 24.7, 22.8, 17.3, 11.1, 10.6; 1H NMR (600 MHz, CDCl3, 333 K): 5.46 (t, J = 7.6 Hz,
1H), 5.004.86 (br, 1H), 4.82 (d,J= 6.9 Hz, 2H), 3.663.41 (br, 2H), 2.662 (s, 3H), 2.657 (s, 3H),
2.362.19 (br, 1H), 2.182.01 (m, 2H), 1.961.88 (m, 1H), 1.77 (s, 3H), 1.76 (s, 3H), 1.33 (s, 9H);13C
NMR (150 MHz, CDCl3, 333 K): 164.0, 162.3, 155.5, 154.2, 150.0, 138.9, 128.8, 124.8, 118.8, 80.0,
61.8, 54.8, 46.6, 32.4, 28.3, 25.6, 23.9, 19.0, 17.1, 12.1, 11.7; HRMS (DART) m/z calcd for
C23H31N3O6 [MH]+: 446.22911, found 446.22896. []D
21 = 49 (c = 0.95, CHCl3)
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10.1H and
13C NMR Spectra
1H NMR (400 MHz, CDCl3) of 2e:
9.0
8.0
7
.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.197
8.196
8.194
8.192
7.497
7.414
7.412
7.3937.191
6.877
6.875
6.872
6.870
2.11
2.071.15
1.02
1.00
0.99
O
O
PhO
2e
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13C NMR (100 MHz, CDCl3) of 2e:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
1
00.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
161.553
150.555
148.811
144.184
129.631
126.068
121.833
119.026
110.222
O
O
PhO
2e
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1H NMR (400 MHz, CDCl3) of 2g:
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3
.0
2.0
1.0
0
8.876
8.861
8.020
8.004
7.458
7.437
7.312
7.264
7.261
7.239
7.236
7.222
7.219
7.217
3.49
2.02
2.00
1.98
N
O
PhO
2g
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13C NMR (100 MHz, CDCl3) of 2g:
X:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
163.922
150.999
150.637
136.979
129.807
126.526
123.350
121.547
N
O
PhO
2g
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1H NMR (400 MHz, CDCl3) of 2h:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.863
8.861
8.858
8.857
8.851
8.849
8.847
8.845
8.293
8.273
7.918
7.9147.443
7.441
7.422
7.289
7.277
7.274
7.270
7.256
7.253
3.17
2.07
1.02
1.02
1.01
1.00
N
O
PhO
2h
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13C NMR (100 MHz, CDCl3) of 2h:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
1
00.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
164.018
151.047
150.255
147.651
137.351
129.654
127.546
126.287
125.992
121.805
N
O
PhO
2h
-
7/29/2019 Ja306062c Si 002-Bzoxozale
26/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S26
1H NMR (400 MHz, CDCl3) of 2i:
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3
.0
2.0
1.0
0
9.475
8.852
8.849
8.824
8.821
7.4837.464
7.444
7.338
7.336
7.318
7.301
7.298
7.289
7.269
3.14
2.05
1.131.01
1.00
N
NO
PhO
2i
-
7/29/2019 Ja306062c Si 002-Bzoxozale
27/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S27
13C NMR (100 MHz, CDCl3) of 2i:
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
10
0.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
62.674
50.574
48.265
46.924
44.778
43.140
29.794
26.623
21.565
N
NO
PhO
2i
-
7/29/2019 Ja306062c Si 002-Bzoxozale
28/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S28
1H NMR (400 MHz, CDCl3) of 2j:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.875
8.853
8.647
8.285
8.260
8.239
7.804
7.800
7.651
7.565
7.544
7.520
7.501
7.482
7.341
7.338
7.316
3.04
3.00
2.982.03
1.01
1.00
1.00
0.98
N
O
PhO
Ph
2j
-
7/29/2019 Ja306062c Si 002-Bzoxozale
29/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S29
13C NMR (100 MHz, CDCl3) of 2j:
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100
.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
164.916
156.926
150.708
149.539
138.819
134.757
130.609
130.235
129.995
129.871
129.143
128.300
127.648
126.556
125.445
124.247
121.814
121.028
N
O
PhO
Ph
2j
-
7/29/2019 Ja306062c Si 002-Bzoxozale
30/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S30
1H NMR (400 MHz, CDCl3) of 2k:
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.350
8.055
8.051
8.041
8.033
8.031
7.476
7.469
7.460
7.433
7.413
7.277
7.274
7.271
7.252
7.250
5.03
3.08
2.04
1.00
S
N
O
PhO Ph
2k
-
7/29/2019 Ja306062c Si 002-Bzoxozale
31/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S31
13C NMR (100 MHz, CDCl3) of 2k:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
1
00.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
169.323
159.867
150.727
147.240
132.764
130.982
129.622
129.152
128.779
127.141
126.182
121.785
S
N
O
PhO Ph
2k
-
7/29/2019 Ja306062c Si 002-Bzoxozale
32/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S32
1H NMR (400 MHz, CDCl3) of 1A-
13C:
abundance
01.02.03.04.05.0X:partsperMillion:1H
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.393
7.812
7.799
7.793
7.609
7.607
7.6027.593
7.587
7.585
7.424
7.420
7.406
7.401
7.397
7.389
7.382
7.378
7.374
7.359
2.08
2.01
1.00
O
13C
N
H
1A-13C
-
7/29/2019 Ja306062c Si 002-Bzoxozale
33/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S33
13C NMR (100 MHz, CDCl3) of 1A-
13C:
abundance
01.02.03.0X:arts
erMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
152.605
150.066
150.037
140.131
140.093
125.694
124.678
120.731
120.664
111.074
111.036
O
13C
N
H
1A-13C
-
7/29/2019 Ja306062c Si 002-Bzoxozale
34/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S34
1H NMR (400 MHz, CDCl3) of 3Ab:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
7.899
7.896
7.890
7.886
7.540
7.537
7.527
7.524
7.335
7.333
7.323
7.321
7.311
7.309
7.174
7.165
7.162
7.152
2.03
2.031.00
1.00
1.00
N
O S
3Ab
-
7/29/2019 Ja306062c Si 002-Bzoxozale
35/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S35
13C NMR (100 MHz, CDCl3) of 3Ab:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
159.115
150.503
142.081
130.331
130.017
129.730
128.338
125.162
124.800
119.888
110.512
N
O S
3Ab
-
7/29/2019 Ja306062c Si 002-Bzoxozale
36/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S36
1H NMR (400 MHz, CDCl3) of 3Ac:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.196
8.194
8.189
8.187
7.802
7.799
7.789
7.787
7.7367.349
7.343
7.340
7.335
7.332
7.326
2.12
1.08
1.05
1.04
1.04
1.00
N
OS
3Ac
-
7/29/2019 Ja306062c Si 002-Bzoxozale
37/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S37
13C NMR (100 MHz, CDCl3) of 3Ac:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
159.800
150.440
142.038
129.354
128.166
127.102
126.709
125.100
124.678
119.994
110.567
N
OS
3Ac
-
7/29/2019 Ja306062c Si 002-Bzoxozale
38/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S38
1H NMR (400 MHz, CDCl3) of 3Ad:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
7.774
7.678
7.676
7.673
7.371
7.364
7.361
7.357
7.353
7.347
7.2877.278
6.630
6.625
6.621
6.616
2.13
1.04
1.03
1.000.96
1.04
N
O O
3Ad
-
7/29/2019 Ja306062c Si 002-Bzoxozale
39/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S39
13C NMR (100 MHz, CDCl3) of 3Ad:
X
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
155.377
150.226
145.830
142.701141.729
125.372
124.943
120.231
114.366
112.353
110.656
N
O O
3Ad
-
7/29/2019 Ja306062c Si 002-Bzoxozale
40/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S40
1H NMR (400 MHz, CDCl3) of 3Ae:
9.0
8.0
7.
0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.217
8.215
7.724
7.712
7.543
7.539
7.535
7.531
7.339
7.329
7.327
7.319
7.317
7.028
7.024
2.09
2.06
1.03
1.02
1.00
N
OO
3Ae
-
7/29/2019 Ja306062c Si 002-Bzoxozale
41/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S41
13C NMR (100 MHz, CDCl3) of 3Ae:
1
80.0
170.0
160.0
150.0
140
.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
158.411
150.296
144.462
144.404141.856
125.042
124.630
119.764
115.520
110.461
109.043
N
OO
3Ae
-
7/29/2019 Ja306062c Si 002-Bzoxozale
42/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S42
1H NMR (400 MHz, CDCl3) of 3Af:
10.0
9.0
8
.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
9.492
9.488
9.483
8.782
8.780
8.770
8.768
8.526
8.522
7.820
7.808
7.797
7.627
7.615
7.415
7.412
7.409
7.402
7.395
7.391
2.121.06
1.06
1.05
1.03
1.01
1.00
N
N
O
3Af
-
7/29/2019 Ja306062c Si 002-Bzoxozale
43/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S43
13C NMR (100 MHz, CDCl3) of 3Af:
:partsperMillion:13C
180.0
170.0
160.0
150.0
1
40.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
160.748
152.136
150.823
150.785
148.878148.850
141.856
141.837
134.757
125.780
124.995
123.969
123.768
123.720
123.174
120.396
120.319
110.864
110.825
N
N
O
3Af
-
7/29/2019 Ja306062c Si 002-Bzoxozale
44/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S44
1H NMR (400 MHz, CDCl3) of 3Ag:
9.0
8.0
7
.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.815
8.811
8.804
8.800
8.069
8.064
8.057
8.053
7.803
7.798
7.612
7.595
7.420
7.415
7.409
7.403
7.396
7.390
2.00
1.94
1.93
0.97
0.92
N
N
O
3Ag
-
7/29/2019 Ja306062c Si 002-Bzoxozale
45/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S45
13C NMR (100 MHz, CDCl3) of 3Ag:
:partsperMillion:13C
180.0
170.0
160.0
150.0
14
0.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
160.622
150.875
150.780
141.776
134.328
126.354
125.172
121.013
120.727
110.989
N
N
O
3Ag
-
7/29/2019 Ja306062c Si 002-Bzoxozale
46/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S46
1H NMR (400 MHz, CDCl3) of 3Ah:
9.0
8.0
7
.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.825
8.814
8.367
8.347
7.900
7.880
7.861
7.843
7.826
7.821
7.678
7.660
7.457
7.444
7.437
7.426
7.4137.409
7.401
7.399
7.389
3.08
2.26
1.01
1.00
0.97
N
N
O
3Ah
-
7/29/2019 Ja306062c Si 002-Bzoxozale
47/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S47
13C NMR (100 MHz, CDCl3) of 3Ah:
X
:arts
erMillion:13C
180.0
170.0
160.0
150.0
14
0.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
161.538
151.142
150.389
146.163
141.872
137.170
126.135
125.648
125.019
123.531
120.727
111.323
N
N
O
3Ah
-
7/29/2019 Ja306062c Si 002-Bzoxozale
48/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S48
1H NMR (400 MHz, CDCl3) of 3Ai:
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
9.582
9.579
8.775
8.769
8.766
8.739
8.733
7.873
7.856
7.6917.687
7.669
7.455
7.451
7.441
7.436
7.431
7.422
7.419
2.06
2.01
1.10
1.00
0.99
N
NN
O
3Ai
-
7/29/2019 Ja306062c Si 002-Bzoxozale
49/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S49
13C NMR (100 MHz, CDCl3) of 3Ai:
:partsperMillion:13C
180.0
170.0
160.0
150.0
1
40.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
159.369
151.043
146.167
144.711144.653
142.019
141.588
126.700
125.339
121.028
111.323
N
NN
O
3Ai
-
7/29/2019 Ja306062c Si 002-Bzoxozale
50/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S50
1H NMR (400 MHz, CDCl3) of 3Aj:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
9.455
9.433
8.725
8.295
8.277
7.926
7.716
7.713
7.698
7.696
7.577
7.557
7.526
7.507
7.462
7.446
3.09
3.01
2.07 2.02
1.01
1.00
0.990.98
N
N
O
Ph3Aj
-
7/29/2019 Ja306062c Si 002-Bzoxozale
51/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S51
13C NMR (100 MHz, CDCl3) of 3Aj:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
1
00.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
161.017
156.926
150.373
149.511
142.210
139.097131.940
130.599
130.216
129.852
129.095
128.079
127.677
126.499
126.278
125.157
123.692
121.019
119.630
110.998
N
N
O
Ph3Aj
-
7/29/2019 Ja306062c Si 002-Bzoxozale
52/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S52
1H NMR (400 MHz, CDCl3) of 3Ak:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
8.218
8.213
8.108
8.102
8.098
8.094
8.091
7.483
7.478
7.474
7.470
7.467
7.395
7.393
7.386
7.3837.379
7.376
3.172.11
2.09
1.05
1.04
1.00
SN
O
3Ak
NPh
-
7/29/2019 Ja306062c Si 002-Bzoxozale
53/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S53
13C NMR (100 MHz, CDCl3) of 3Ak:
:arts
erMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
169.965
158.363
150.641
144.538
141.875
132.822
130.925
129.124
127.160
125.684
124.966
122.322
120.597
110.988
SN
O
3Ak
NPh
-
7/29/2019 Ja306062c Si 002-Bzoxozale
54/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S54
1H NMR (400 MHz, CDCl3) of 2Cf:
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
9.181
9.177
8.649
8.641
8.637
8.237
8.221
8.217
8.047
7.414
7.404
7.399
7.394
7.385
7.372
7.364
7.353
7.352
4.19
2.09
1.02
1.01
1.01
1.00
N
N
SPh
3Cf
-
7/29/2019 Ja306062c Si 002-Bzoxozale
55/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S55
13C NMR (100 MHz, CDCl3) of 3Cf:
:partsperMillion:13C
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
163.450
150.737
147.575
140.285
139.509
133.310
130.934
129.679
129.219
128.664
126.767
123.759
N
N
SPh
3Cf
-
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56/65
Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S56
1H NMR (400 MHz, C6D6) of 4:
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0
1.9501.918
1.719
1.696
1.678
1.645
1.591
1.359
1.316
1.293
1.259
1.228
1.197
1.171
1.150
1.127
24.00
20.14
2.182.00
Ni
PP
OC CO
Ni(dcype)(CO)2 (4)
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S57
13C NMR (100 MHz, C6D6) of 4:
X:partsperMillion:13C
210.0
200.0
190.0
180.0
170.0
160.0
150.0
140.0
130.0
120.0
110.0
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0
205.038
35.840
35.754
35.677
29.344
28.520
27.591
27.534
27.467
27.409
26.68123.376
23.175
22.983
NiPP
OC CO
Ni(dcype)(CO)2 (4)
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S58
1H NMR (600 MHz, DMSO-d
6, 373 K) of phenyl ester 8
O
N
BocN
O
PhO Me
phenyl ester 8
H
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S59
13C NMR (150 MHz, DMSO-d
6, 373 K) of phenyl ester 8
O
N
BocN
O
PhO
Me
phenyl ester 8
H
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S60
1H NMR (600 MHz, DMSO-d
6, 373 K) of methyl ester 9
N
OMe
O
OMe
O
N
Me
N
t-BuO
O
9
H
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S61
13C NMR (150 MHz, DMSO-d
6, 373 K) of methyl ester 9
N
OMe
O
OMe
O
N
Me
N
t-BuO
O
9
H
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S62
1H NMR (600 MHz, DMSO-d
6, 373 K) of prenyl ester 10
10
O
N
Me
N
O
N
Me
O
O
O
t-BuO
HMeMe
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S63
13C NMR (150 MHz, DMSO-d
6, 373 K) of prenyl ester 10
10
O
N
Me
N
O
N
Me
O
O
O
t-BuO
HMeMe
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
S64
1H NMR (600 MHz, CDCl3, 333 K) of prenyl ester 10
10
O
N
Me
N
O
N
Me
O
O
O
t-BuO
HMeMe
-
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Supporting Information (Amaike, Muto, Yamaguchi, Itami)Decarbonylative CH Coupling of Azoles and Aryl Esters
13C NMR (150 MHz, CDCl3, 333 K) of prenyl ester 10
10
O
N
Me
N
O
N
Me
O
O
O
t-BuO
HMeMe