老挝黄金赌场深圳先进技术研究院殷勤团队报道了，光诱导Pd催化丁二烯1,2-双官能化催化吲哚的不对称级联脱芳化反应。相关研究成果发表在2024年4月20日出版的《德国应用化学》。

使用易得的有机卤化物和亲核试剂光诱导Pd催化丁二烯双官能化，代表了一种新兴且有吸引力的方法，用于组装在烯丙基位置具有各种官能团的多功能烯烃。然而，由于开壳过程，C-C或C-X键形成步骤中的对映控制和/或非对映控制尚未解决。

该文中，研究人员提出了一种吲哚的级联不对称脱芳反应，通过光激发的Pd催化1,3-丁二烯的1,2-双碳官能化，其中在丁二烯的光诱导双官能化中首次实现了对亲核和亲电部分的不对称控制。

该方法提供了结构新颖的手性螺吲哚啉，其具有两个连续的立体发生中心，具有高的非对映体比率（高达>20:1 dr）和良好到优异的对映体比例（高达97:3 er）。

对该机制的实验和计算研究已经证实了，一种涉及激发态钯催化的自由基途径。研究人员发现基质和催化剂之间的，排列和非共价相互作用对立体控制至关重要。

附：英文原文

Title: Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd-Catalyzed 1,2-Bisfunctionalization of Butadienes

Author: Xiaohang Zhan, Zhiwen Nie, Na Li, Ao Zhou, Haotian Lv, Mingrong Liang, Keqin Wu, Guijuan Cheng, Qin Yin

Issue&Volume: 2024-04-20

Abstract: Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and a nucleophile represents an emerging and attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in the C-C or C-X bond-formation step have not been solved due to the open-shell process. Herein, we present a cascade asymmetric dearomatization reaction of indoles via photoexcited Pd-catalyzed 1,2-biscarbonfunctionalization of 1,3-butadienes, wherein asymmetric control on both the nucleophile and electrophile part is achieved for the first time in photoinduced bisfunctionalization of butadienes. This method delivers structurally novel chiral spiroindolenines bearing two contiguous stereogenic centers with high diastereomeric ratios (up to >20:1 dr) and good to excellent enantiomeric ratios (up to 97:3 er). Experimental and computational studies of the mechanism have confirmed a radical pathway involving excited-state palladium catalysis. The alignment and non-covalent interactions between the substrate and the catalyst were found to be essential for stereocontrol.

DOI: 10.1002/anie.202404388

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202404388