Organocatalytic asymmetric arylation of indoles enabled by azo groups

Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin

2018-01

10.1038/NCHEM.2866

Nature Chemistry   影响因子和分区

1755-4330

1755-4349

Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

SCI ; IC ; CCR

英语

ESI高被引

第一 ; 通讯

Shenzhen special funds for the development of biomedicine, the Internet, new energy and new material industries[JCYJ20150430160022510]

Chemistry

Chemistry, Multidisciplinary

WOS:000423143500013

NATURE PUBLISHING GROUP

Web of Science

South Univ Sci & Technol China, Dept Chem, Shenzhen 518055, Peoples R China

Qi, Liang-Wen,Mao, Jian-Hui,Zhang, Jian,et al. Organocatalytic asymmetric arylation of indoles enabled by azo groups[J]. Nature Chemistry,2018,10(1):58-64.

Qi, Liang-Wen,Mao, Jian-Hui,Zhang, Jian,&Tan, Bin.(2018).Organocatalytic asymmetric arylation of indoles enabled by azo groups.Nature Chemistry,10(1),58-64.

Qi, Liang-Wen,et al."Organocatalytic asymmetric arylation of indoles enabled by azo groups".Nature Chemistry 10.1(2018):58-64.