Brägger Yannick, Green Ori, Bhawal Benjamin N, Morandi Bill
ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland.
School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, U.K.
J Am Chem Soc. 2023 Sep 13;145(36):19496-19502. doi: 10.1021/jacs.3c05680. Epub 2023 Aug 28.
Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determine the thermodynamically favored product of the reaction and the kinetic selectivity observed. With the distinct selectivity profile of our ketone chain-walking process, the isomerization of various steroids was demonstrated to rapidly access novel steroids with "unnatural" oxidation patterns.
在此，描述了一种以类似于烯烃链行走反应的方式对酮进行异构化的方法。使用广泛可得且廉价的吡咯烷和元素硫作为催化剂来实现这种可逆转化。该方法实用性的关键在于阐明一种立体化学模型，以确定反应的热力学有利产物以及观察到的动力学选择性。凭借我们酮链行走过程独特的选择性特征，已证明各种甾体的异构化能够快速获得具有“非天然”氧化模式的新型甾体。
