钌-BINAP 催化醇 C-H 叔戊烯基化反应：通过 1,3-烯炔转移氢化实现对映选择性羰基丙炔化反应中化学计量碳负离子的超越。
Ruthenium-BINAP Catalyzed Alcohol C-H tert-Prenylation via 1,3-Enyne Transfer Hydrogenation: Beyond Stoichiometric Carbanions in Enantioselective Carbonyl Propargylation.
机构信息
University of Texas at Austin , Department of Chemistry, Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2016 Apr 27;138(16):5238-41. doi: 10.1021/jacs.6b02279. Epub 2016 Apr 15.
Abstract
The chiral ruthenium complex formed in situ from (TFA)2Ru(CO)(PPh3)2 and (R)-BINAP is found to catalyze the enantioselective C-C coupling of diverse primary alcohols with the 1,3-enyne, TMSC≡CC(Me)═CH2, to form secondary homopropargyl alcohols bearing gem-dimethyl groups. All reagents for this byproduct-free coupling are inexpensive and commercially available, making this protocol a practical alternative to stoichiometric carbanions in enantioselective carbonyl reverse prenylation.
摘要
由 (TFA)2Ru(CO)(PPh3)2 和 (R)-BINAP 原位形成的手性钌配合物被发现能够催化各种伯醇与 1,3-炔、TMSC≡CC(Me)═CH2 的对映选择性 C-C 偶联，形成带有偕二甲基的仲同型丙炔醇。此无副产物偶联反应所需的所有试剂均价格低廉且市售可得，使得该方法成为对映选择性羰基反转烯丙基化中当量碳负离子的实用替代方案。
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