Synlett 2025; 36(08): 963-969
BMIDA-Directed Catalytic Asymmetric Transfer Hydrogenation for Enantioselective Access to α-Boryl Alcohols
Shuang Yang
,
Xinqiang Fang∗
This work was supported by the National Natural Science Foundation of China (No. 22071242 and 21871260), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000), the Natural Science Foundation of Fujian Province (No. 2021J01522), and the Self-deployment Project Research Program of Haixi Institutes, Chinese Academy of Sciences (CXZX-2022-GH03).
Abstract
The quest for general and highly efficient and enantioselective catalytic route to chiral alcohols remains a formidable challenge in asymmetric synthesis. Here, we highlight our recent work of asymmetric transfer hydrogenation (ATH) of N -methyliminodiacetyl (MIDA) acylboronates, showcasing a versatile platform for the efficient synthesis of enantiomerically enriched secondary alcohols. Acyl-MIDA-boronates harboring diverse (het)aryl, alkyl, alkynyl, alkenyl, and carbonyl substituents can be hydrogenated, yielding various α-borylated alcohols with high ee values. Crucially, the boron moiety can be easily transformed into other groups, allowing access to previously unattainable carbinols adorned with two structurally similar substituents. The enantioselectivity-directing role of BMIDA is elucidated by computational analyses, which stems from the CH–O electrostatic attraction between the η6 -arene-CH of the catalyst and the σ-bonded oxygen atoms within BMIDA. This work represents the first asymmetric transformation on acylboronates and expands the domain of asymmetric transfer hydrogenation.
Key words
asymmetric transfer hydrogenation -
BMIDA -
acylboronate -
dicarbonyl boronate -
α-boryl alcohol
Publication History
Received: 23 September 2024
© 2024. Thieme. All rights reserved
Georg Thieme Verlag KG
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