中国科学院化学研究所Qing-Hua Fan研究小组取得一项新突破。他们的最新研究利用钌催化实现了9-菲酚的对映选择性加氢反应。相关论文于2022年6月29日发表在《德国应用化学》杂志上。
在这项工作中，通过捕获不稳定的酮互变异构体，课题组首次在温和的条件下成功地实现了钌催化的9-菲酚高效对映选择性加氢。该方法可方便地获得一系列手性9,10-二氢菲-9-醇，收率高达98%且ee值大于99%。这一加氢途径包括碱促进的9-菲酚的互变异构化，以及对原位生成的不稳定酮互变异构体的钌催化不对称加氢。
据介绍，对芳香醇进行对映选择性氢化以生成相应的手性环醇仍然是一个挑战，这是由其芳香性和难以控制的区域、化学和立体选择性导致的。
附：英文原文
Title: Ruthenium-Catalyzed Enantioselective Hydrogenation of 9-Phenanthrols
Author: Qing-Hua Fan, Shu-Xin Zhang, Cong Xu, Niannian Yi, Shan Li, Yan-Mei He, Yu Feng
Issue&Volume: 2022-06-29
Abstract: The enantioselective hydrogenation of arenols to corresponding chiral cyclic alcohols remains a challenge because of their aromaticity and the difficulty in controlling the regio-, chemo-, and stereoselectivity. In this work, the first highly efficient ruthenium-catalyzed enantioselective hydrogenation of 9-phenanthrols has been successfully realized under mild conditions via trapping the unstable keto tautomers.The method provides a facile access to a range of chiral 9,10-dihydrophenanthren-9-ols with up to 98% yield and >99% ee . The hydrogenation pathway includes base-promoted tautomerization of 9-phenanthrols and Ru-catalyzed asymmetric hydrogenation of the in situ generated unstable keto tautomers.
DOI: 10.1002/anie.202205739
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202205739
