Direct enolization chemistry of 7-azaindoline amides: A case study of bis(tetrahydrophosphole)-type ligands
Direct enolization chemistry of 7-azaindoline amides: A case study of bis(tetrahydrophosphole)-type ligands
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DOI：
10.1016/j.tet.2018.03.073
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发表时间：
2018-06-28
期刊：
影响因子：
2.1
通讯作者：
Shibasaki, Masakatsu
中科院分区：
文献类型：
--
作者：
Li, Zhao;Noda, Hidetoshi;Shibasaki, Masakatsu
7-氮杂多林酰胺在软Lewis酸/Bronsted碱协同催化中促进了烯醇化反应，因此在直接烯醇化化学中特别有用。(R，R)-Ph-BPE的铜(I)络合物是一种双(四氢膦)型手性双膦配体，无论酰胺的α-取代基的性质如何，都表现出一致的高催化性能和立体选择性。然而，出乎意料的是，烷基取代的双(四氢膦)型配体的催化性能很差。对铜(I)/酰胺和铜(L)/烯醇络合物优化结构的评价为分析转移反应结果提供了线索。(C)2018爱思唯尔有限公司。保留所有权利。
7-Azaindoline amides are particularly useful in direct enolization chemistry due to their facilitated enolization in soft Lewis acid/Bronsted base cooperative catalysis. The Cu(I) complex of (R,R)-Ph-BPE, a bis(tetrahydrophosphole)-type chiral bisphosphine ligand, exhibits consistently high catalytic performance and stereoselectivity irrespective of the nature of the alpha-substituent of the amides. Unexpectedly, however, alkyl-substituted bis(tetrahydrophosphole)-type ligands have substantially inferior catalytic performance. Evaluation of the optimized structures of Cu(I)/amide and Cu(l)/enolate complexes provided clues to dissecting the diverted reaction outcomes. (C) 2018 Elsevier Ltd. All rights reserved.