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DOI: 10.1055/s-0029-1219829
Synthesis of Enantiomerically Pure Oxiranylboronic Esters
Publication History
Publication Date:
13 April 2010 (online)
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Abstract
Enantiomerically pure oxiranylboronic esters were synthesized for the first time starting from readily available alkenylboronic esters. Their absolute configurations were assigned by means of spectroscopic correlations and confirmed by means of X-ray structure analysis.
Key words
boron - chiral auxiliaries - epoxidation - asymmetric synthesis
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References and Notes
Selected Data
for Epoxide 3c
[α]D
²0 -113.5
(c 1.00, CHCl3); mp 178 ˚C.¹³ IR
(film):
νmax = 3437, 2939,
1446, 1383, 1198, 1074, 757, 650 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 1.42
(dd, ³
J
OH,1b = 7.2
Hz, ³
J
OH,1a = 6.0
Hz, 1 H, OH), 1.93 (d, ³
J
3,2 = 3.2
Hz, 1 H, 3-H), 2.93 (ddd, ³
J
2,1b = 4.7
Hz, ³
J
2,3 = 3.2
Hz, ³
J
2,1a = 2.6
Hz, 1 H, 2-H), 3.02 (s, 6 H, OCH3), 3.39 (ddd, ²
J
1b,1a = 12.1
Hz, ³
J
1b,OH = 7.1
Hz, ³
J
1b,2 = 4.8
Hz, 1 H, 1-Hb), 3.77 (ddd, ²
J
1a,1b = 12.5
Hz, ³
J
1a,OH = 5.8
Hz, ³
J
1a,2 = 2.5
Hz, 1 H, 1-Ha), 5.41 (s, 2 H, 4′-H, 5′-H),
7.26-7.35 (m, 20 H, arom. CH). ¹³C
NMR (151 MHz, CDCl3): δ = 40.6
(C-3), 52.0 (OCH3), 56.3 (C-2), 62.8 (C-1), 78.5 (C-4′,
C-5′), 83.4 (CPh2OMe), 127.6, 127.8, 127.9,
128.1, 128.6, 129.8 (arom. CH), 140.9, 141.0 (arom. Cipso).
ESI-MS (+): m/z (%) = 559.1
(17) [M + Na]+, 453.4
(95), 333.0(100). Anal. Calcd (%) for C33H33BO6 (536.4):
C, 73.89; H, 6.20. Found: C, 73.69; H, 6.28.
Selected Data for Epoxide 4a
[α]D
²0 -108.9
(c 1.02, CHCl3). IR (film): νmax = 2932,
1494, 1446, 1383, 1197, 1077, 758, 700 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 0.85
(t, ³
J
7,6 = 7.0
Hz, 3 H, 7-H), 1.20-1.41 (m, 8 H, 3-H, 4-H, 5-H, 6-H),
1.59 (d, ³
J
1,2 = 3.0
Hz, 1 H, 1-H), 2.29 (mc, 1 H, 2-H), 3.01 (s, 6 H, OCH3),
5.37 (s, 2 H, 4′-H, 5′-H), 7.24-7.39
(m, 20 H, arom. CH). ¹³C NMR (151 MHz, CDCl3): δ = 14.1
(C-7), 22.7 (C-6), 26.1 (C-5), 31.8 (C-4), 33.7 (C-3), 43.8 (C-1),
51.9 (OCH3), 56.5 (C-2), 78.1 (C-4′, C-5′),
83.3 (CPh2OMe), 127.5, 127.6, 127.8, 128.1, 128.7, 129.8
(arom. CH), 141.0, 141.0 (arom. Cipso). ESI-MS (+): m/z (%) = 593.7
(63) [M + H2O]+,
575.4 (90), 522.8 (35), 397.6 (33), 379.2 (49), 355.4 (100). Anal.
Calcd (%) for C37H41BO5 (576.5):
C, 77.08; H, 7.17. Found: C, 76.90; H, 7.28.
Selected Data for Epoxide 4b
[α]D
²0 -40.2
(c 1.42, CHCl3). IR (film): νmax = 2938,
1494, 1446, 1380, 1198, 1075, 755, 700 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 1.95
(d, ³
J
1,2 = 2.8
Hz, 1 H, 1-H), 3.04 (s, 6 H, OCH3), 3.18 (d, ³
J
2,1 = 2.8
Hz, 1 H, 2-H), 5.42 (s, 2 H, 4′-H, 5′-H), 7.10-7.42
(m, 25 H, arom. CH). ¹³C NMR (151 MHz, CDCl3):
d = 49.2 (C-1), 51.9 (OCH3),
56.2 (C-2), 78.2 (C-4′, C-5′), 83.3 (CPh2OMe),
125.6, 127.6, 127.7, 127.9, 128.1, 128.5, 128.7, 129.8 (arom. CH),
138.4, 140.9, 141.1 (arom. Cipso). ¹¹B
NMR (192 MHz, CDCl3): δ = 31.24.
ESI-MS (+): m/z (%) = 599.3
(37) [M + H2O]+,
582.2 (80), 539.2 (82), 453.2 (100), 426.5 (99), 317.2 (75), 197.3
(76). Anal. Calcd (%) for C38H35BO5 (582.5):
C, 78.35; H, 6.06. Found: C, 78.11; H, 6.16.
Selected Data for Epoxide 4c
[α]D
²0 -136.7
(c 1.05, CHCl3). IR (film): νmax = 3448,
2938, 1446, 1381, 1198, 1075, 758, 650 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 1.42
(dd, ³
J
OH,1b = 7.0
Hz, ³
J
OH,1a = 5.9
Hz, 1 H, OH), 1.88 (d, ³
J
3,2 = 3.0
Hz, 1 H, 3-H), 2.50 (ddd, ³
J
2,1b = 4.5 Hz, ³
J
2,3 = 3.0
Hz, ³
J
2,1a = 2.5
Hz, 1 H, 2-H), 3.02 (s, 6 H, OCH3), 3.38 (ddd, ²
J
1b,1a = 12.1
Hz, ³
J
1b,OH = 7.2
Hz, ³
J
1b,2 = 4.8
Hz, 1 H, 1-Hb), 3.77 (ddd, ²
J
1a,1b = 12.4
Hz, ³
J
1a,OH = 5.7
Hz, ³
J
1a,2 = 2.4
Hz, 1 H, 1-Ha), 5.40 (s, 2 H, 4′-H, 5′-H),
7.24-7.39 (m, 20 H, arom. CH). ¹³C
NMR (151 MHz, CDCl3): δ = 40.6
(C-3), 51.9 (OCH3), 56.0 (C-2),
62.6 (C-1), 78.2 (C-4′, C-5′), 83.3 (CPh2OMe),
127.5, 127.6, 127.9, 128.1, 128.7, 129.8 (arom. CH), 140.9, 141.0
(arom. Cipso). ESI-MS (+): m/z (%) = 559.1
(17) [M + Na]+, 453.4 (95),
333.0(100). Anal. Calcd (%) for C33H33BO6 (536.4):
C, 73.89; H, 6.20. Found: C, 73.67; H, 6.31.
CCDC-766999 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/deposit [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax +44 (1223)336033; email: deposit@ccdc.cam.ac.uk].