Department of Chemistry, University of Chicago, Chicago, IL 60637, USA.
Korea Research Institute of Chemical Technology, 141, Gajeong-ro, Yuseong-gu, Daejeon, 34114, South Korea.
Angew Chem Int Ed Engl. 2018 Jan 8;57(2):475-479. doi: 10.1002/anie.201711394. Epub 2017 Dec 8.
A rhodium-catalyzed intramolecular acetyl-group transfer has been achieved through a "cut and sew" process. The challenge arises from the existence of different competitive pathways. Preliminary success has been achieved with unstrained enones that contain a biaryl linker. The use of an electron-rich N-heterocycilc carbene (NHC) ligand is effective to inhibit undesired β-hydrogen elimination. Various 9,10-dihydrophenanthrene derivatives can be prepared with excellent functional-group compatibility. The C-labelling study suggests that the reaction begins with cleavage of the unstrained C-C bond, followed by migratory insertion and reductive elimination.
铑催化的分子内乙酰基转移通过“切和缝”过程实现。挑战来自于存在不同的竞争途径。初步成功已应用于含有联苯连接基的非张力烯酮。使用富电子的 N-杂环卡宾(NHC)配体可有效抑制不需要的β-氢消除。各种 9,10-二氢菲衍生物可以通过优异的官能团兼容性制备。C 标记研究表明,反应首先从非张力 C-C 键的断裂开始,然后进行迁移插入和还原消除。