Synthesis of Enantiomerically
Pure Oxiranylboronic Esters

Enrique Fernández; Wolfgang Frey; Jörg Pietruszka

doi:10.1055/s-0029-1219829

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Synlett 2010(9): 1386-1388
DOI: 10.1055/s-0029-1219829

LETTER

Synthesis of Enantiomerically Pure Oxiranylboronic Esters

Enrique Fernández^a, Wolfgang Frey^b, Jörg Pietruszka*^a
^a Institut für Bioorganische Chemie der Heinrich-Heine-Universität Düsseldorf im Forschungszentrum Jülich, Im Stetternicher Forst, Geb. 15.8, 52426 Jülich, Germany
Fax: +49(2461)616196; e-Mail: j.pietruszka@fz-juelich.de;
^b Institut für Organische Chemie der Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany

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Publication History

Received 5 March 2010
Publication Date:
13 April 2010 (online)

Abstract
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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

References and Notes

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Selected Data for Epoxide 3c
[α]_D ^²0 -113.5 (c 1.00, CHCl₃); mp 178 ˚C.^¹³ IR (film):
ν_max = 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-H_b), 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-H_a), 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. C_ipso). 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): ν_max = 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 (m_c, 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. C_ipso). 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): ν_max = 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. C_ipso). ^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): ν_max = 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-H_b), 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-H_a), 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. C_ipso). 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.

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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].