Enantioselective Synthesis of Allylboronates and Allylic Alcohols by Copper-Catalyzed 1,6-Boration

Chiral secondary allylboronates are obtained in high enantioselectivities and 1,6:1,4 ratios by the copper‐catalyzed 1,6‐boration of electron‐deficient dienes with bis(pinacolato)diboron (B2(pin)2). The reactions proceed efficiently using catalyst loadings as low as 0.0049 mol %. The allylboronates...

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Bibliographic Details
Published in	Angewandte Chemie International Edition Vol. 53; no. 16; pp. 4186 - 4190
Main Authors	Luo, Yunfei, Roy, Iain D., Madec, Amaël G. E., Lam, Hon Wai
Format	Journal Article
Language	English
Published	Weinheim WILEY-VCH Verlag 14.04.2014 WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc
Edition	International ed. in English
Subjects	1,6‐addition 6-addition Alcohols Aldehydes Allyl compounds asymmetric catalysis boron Boron - chemistry Catalysis Catalysts Chemical reactions Chemistry Chemistry, Multidisciplinary Copper Copper - chemistry Dienes enantioselectivity Molecular Structure Oxidation Physical Sciences Propanols - chemistry Science & Technology Stereoisomerism Synthesis enantioselectivity REAGENTS HOMOALLYLIC ALCOHOLS EFFICIENT ROUTE ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS asymmetric catalysis 1,6-ADDITION 1 KETONES ESTERS copper 6-addition boron CONJUGATE ADDITIONS ASYMMETRIC BETA-BORATION DIBORON 1,6-addition
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ISSN	1433-7851 1521-3773 1521-3773
DOI	10.1002/anie.201310380

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Summary:	Chiral secondary allylboronates are obtained in high enantioselectivities and 1,6:1,4 ratios by the copper‐catalyzed 1,6‐boration of electron‐deficient dienes with bis(pinacolato)diboron (B2(pin)2). The reactions proceed efficiently using catalyst loadings as low as 0.0049 mol %. The allylboronates may be oxidized to the allylic alcohols, and can be used in stereoselective aldehyde allylborations. This process was applied to a concise synthesis of atorvastatin, in which the key 1,6‐boration was performed using only a 0.02 mol % catalyst loading. 1,6‐Borations of electron‐deficient dienes with bis(pinacolato)diboron using copper catalyst loadings as low as 0.0049 mol % provided chiral allylboronates that, after oxidation, result in allylic alcohols in high enantioselectivities and 1,6:1,4 ratios. The allylboronates can also be used in stereoselective allylations of aldehydes. This process was applied to a concise synthesis of atorvastatin.
Bibliography:	We thank the ERC (Starting Grant No. 258580), the EPSRC (Leadership Fellowship to H.W.L.), Pfizer, AstraZeneca, and the University of Edinburgh for support. We thank Xiaoming Yang of Shanghai Chiral Chemistry Co., Ltd. for providing starting materials and NMR data for atorvastatin (13). We are grateful to Dr. Gary S. Nichol (University of Edinburgh) for X-ray crystallography, and the EPSRC National Mass Spectrometry Facility for high-resolution mass spectra. We thank Dr. Ai-Lan Lee at Heriot-Watt University for the use of a polarimeter. ark:/67375/WNG-4FKQRS7J-9 ArticleID:ANIE201310380 EPSRC - No. Pfizer; No. AstraZeneca; No. University of Edinburgh ERC - No. 258580 istex:4461B2776AD0825ECF7DA6CF81C1960AFBB9E10C 13 We thank the ERC (Starting Grant No. 258580), the EPSRC (Leadership Fellowship to H.W.L.), Pfizer, AstraZeneca, and the University of Edinburgh for support. We thank Xiaoming Yang of Shanghai Chiral Chemistry Co., Ltd. for providing starting materials and NMR data for atorvastatin We are grateful to Dr. Gary S. Nichol (University of Edinburgh) for X‐ray crystallography, and the EPSRC National Mass Spectrometry Facility for high‐resolution mass spectra. We thank Dr. Ai‐Lan Lee at Heriot‐Watt University for the use of a polarimeter. researchfish UKRI European Research Council (ERC) ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.201310380