对映选择性烯烃异构化。

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2026-05-01 DOI:10.1021/jacs.6c04825

Bianca L Imbriaco, Sumin Lee, Eve Yuanwei Xu, Kuo Zhao, Robert R Knowles

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引用次数: 0

摘要

报道了一种基于激发态电子转移的烯烃对映选择性反热力学位置异构化的光驱动方法。四取代烯醇醚的连续氧化和去质子化产生烯丙基自由基，该自由基被带有手性生物恶唑啉（BiOX）配体的Cr（II）助催化剂捕获。甲醇对新生的Cr（III）烯丙基络合物进行区域选择性和对映选择性原脱金属反应，最终得到对映选择性高达95:5 er的烯烃产物。动力学和同位素标记研究支持对映体的原脱金属作用，并揭示了在同一催化歧管中存在两个主要的KIEs。

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Enantioselective Contrathermodynamic Olefin Isomerization.

A light-driven method for the enantioselective contrathermodynamic positional isomerization of olefins based on excited-state electron transfer is reported. Sequential oxidation and deprotonation of a tetrasubstituted enol ether generates an allylic radical which is captured by a Cr(II) cocatalyst bearing a chiral bioxazoline (BiOX) ligand. Regio- and enantioselective protodemetalation of the nascent Cr(III) allyl complex by methanol yields the terminal olefin product with enantioselectivities of up to 95:5 er. Kinetic and isotopic labeling studies support an enantiodetermining protodemetalation and reveal the presence of two primary KIEs within the same catalytic manifold.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.