Catalytic remote hydrohalogenation of internal alkenes

Li, Xiang1,2,3; Jin, Jianbo1,2; Chen, Pinhong1,2; Liu, Guosheng1,2,3

2022

10.1038/s41557-021-00869-x

Nature Chemistry   影响因子和分区

1755-4330

1755-4349

Primary alkyl halides have broad utility as fine chemicals in organic synthesis. The direct halogenation of alkenes is one of the most efficient approaches for the synthesis of these halides. Internal alkenes, in particular mixtures of isomers from refineries, constitute readily available and inexpensive feedstock and are the most attractive starting materials for this synthesis. However, the hydrohalogenation of alkenes generally affords branched alkyl halides; there are no catalytic methods to prepare linear alkyl halides directly from internal alkenes, let alone from a mixture of alkene isomers. Here we report the remote oxidative halogenation of alkenes under palladium catalysis via which both terminal and internal alkenes yield primary alkyl halides efficiently. Engineering pyridine-oxazoline ligands by introducing a hydroxyl group is essential for achieving excellent chemo- and regioselectivity. The catalytic system is also good for the mixture of alkene isomers generated from dehydrogenation of alkanes, providing a window to investigate the high-value utilization of inexpensive alkanes.

SCI

英语

NI论文

通讯

National Key R&D Program of China[2021YFA1500100] ; National Natural Science Foundation of China[91956202,21971255,21790330,21821002] ; Science and Technology Commission of Shanghai Municipality["20JC1417000",21520780100,19590750400] ; International Partnership Program[121731KYSB20190016] ; Key Research Program of Frontier Science of the Chinese Academy of Sciences[QYZDJSSW-SLH055] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences[2018292]

Chemistry

Chemistry, Multidisciplinary

WOS:000750332800004

NATURE PORTFOLIO

Web of Science

1.Chinese Acad Sci, Univ Chinese Acad Sci, Ctr Excellence Mol Synth, Shanghai Inst Organ Chem,State Key Lab Organometa, Shanghai, Peoples R China
2.Chinese Acad Sci, Univ Chinese Acad Sci, Ctr Excellence Mol Synth, Shanghai Inst Organ Chem,Shanghai Hongkong Joint, Shanghai, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen, Peoples R China

Li, Xiang,Jin, Jianbo,Chen, Pinhong,et al. Catalytic remote hydrohalogenation of internal alkenes[J]. Nature Chemistry,2022.

Li, Xiang,Jin, Jianbo,Chen, Pinhong,&Liu, Guosheng.(2022).Catalytic remote hydrohalogenation of internal alkenes.Nature Chemistry.

Li, Xiang,et al."Catalytic remote hydrohalogenation of internal alkenes".Nature Chemistry (2022).