Organophotoredox-catalyzed Intermolecular Formal Grob Fragmenta-tion of Cyclic Alcohols with Activated Allylic Acetates

Wubing Zeng^†, Xiaoyu Zhang^†, Yinlei Zhang^†, Shiji Xiao^‡, Yongming Tang^†, Peizhong Xie^*†, and Teck-Peng Loh^*†§¶

^† School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.

^‡ Jiangsu BioGuide Laboratory Co., Ltd, Wujin Economic Development Zone, Changzhou 213000, Jiangsu, China.

^§ College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou, 450001, China.

^¶ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371.

Abstract: We have developed an efficient method that employs organophotoredox-catalyzed relay Grob fragmentation to facilitate the smooth ring-opening allylation of cyclic alcohols in an environmentally-friendly manner. This protocol directly incorporates a wide spectrum of cyclic alcohols and activated allylic acetates into the cross-coupling reaction, eliminating the need for metal catalysts. The process yields a variety of distally unsaturated ketones with good to excellent outcomes and superior stereoselectivity, while acetic acid is the sole byproduct.

Organic Letters 2023, 25, 5869-5874.（影响因子：5.6）

论文链接：https://pubs.acs.org/doi/10.1021/acs.orglett.3c02129