Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and -Ketoesters

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• 作者：Dr. Daniel W. Robbins ; KyungA Lee ; Daniel L. Silverio ; Alexey Volkov ; Dr. Sebastian Torker and Prof. Amir H. Hoveyda
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：August 8, 2016
• 年：2016
• 卷：128
• 期：33
• 页码：9762-9766
• 全文大小：1736K
• ISSN：1521-3757

文摘

A set of broadly applicable methods for efficient catalytic additions of easy-to-handle allyl-B(pin) (pin=pinacolato) compounds to ketones and acyclic α-ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small-molecule aminophenol-based catalysts. Notably, with ketones, increasing the size of a catalyst moiety (tBu to SiPh₃) results in much higher enantioselectivity. With α-ketoesters, on the other hand, not only does the opposite hold true, since Me substitution leads to substantially higher enantioselectivity, but the sense of the selectivity is reversed as well.