Photocatalytic Multisite Functionalization of Unactivated Terminal Alkenes by Merging Polar Cycloaddition and Radical Ring‐Opening Process

Author:

Liu Haidong12,Wang Yi‐Peng1,Wang Hui1,Ren Kewei1,Liu Longfei1,Dang Luzhen1,Wang Cheng‐Qiang1,Feng Chao1ORCID

Affiliation:

1. Technical Institute of Fluorochemistry (TIF) Institute of Advanced Synthesis (IAS) State Key Laboratory of Material-Oriented Chemical Engineering School of Chemistry and Molecular Engineering Nanjing Tech University Nanjing 211816 China

2. Department of Chemistry & Chemical Engineering Gannan Normal University Ganzhou Jiangxi 341000 China

Abstract

AbstractAlthough highly appealing for rapid access of molecular complexity, multi‐functionalization of alkenes that allows incorporation of more than two functional groups remains a prominent challenge. Herein, we report a novel strategy that merges dipolar cycloaddition with photoredox promoted radical ring‐opening remote C(sp3)−H functionalization, thus enabling a smooth 1,2,5‐trifunctionalization of unactivated alkenes. A highly regioselective [3+2] cycloaddition anchors a reaction trigger onto alkene substrates. The subsequent halogen atom transfer (XAT) selectively initiates ring‐opening process, which is followed by a series of 1,5‐hydrogen atom transfer (1,5‐HAT) and intermolecular fluorine atom transfer (FAT) events. With this method, site‐selective introduction of three different functional groups is accomplished and a broad spectrum of valuable β‐hydroxyl‐ϵ‐fluoro‐nitrile products are synthesized from readily available terminal alkenes.

Publisher

Wiley

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