当前位置: X-MOL 学术Angew. Chem. Int. Ed. › 论文详情
Selective C−H Halogenation with a Highly Fluorinated Manganese Porphyrin
Angewandte Chemie International Edition ( IF 11.994 ) Pub Date : 2017-12-28 , DOI: 10.1002/anie.201710676
Gang Li, Andrew K. Dilger, Peter T. Cheng, William R. Ewing, John T. Groves

Abstract

The selective C−H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C−H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-MnV species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step.

Thumbnail image of graphical abstract

A deficiency that's a bonus: A highly electron-deficient manganese porphyrin was found to effectively catalyze the radical halogenation of strained, electron-deficient aliphatic substrates under mild conditions (see scheme). The bulkiness of the catalyst resulted in unique stereo- and regioselectivity.

更新日期:2018-01-03

 

Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
分享到
评论: 1
期刊列表
Wiley论文编辑服务,每月大奖送不停!
深圳大学-同济大学联合招聘博士后(税后年薪30万)
华中师范大学第一届国际青年学者化学科学论坛
【问答】大分子介晶有哪些重要意义?
X-MOL近期新增451种期刊(20171216)
2017年中科院JCR分区化学大类列表
试剂库存管理
化合物查询
down
wechat
bug