Direct Catalytic Asymmetric and Regiodivergent N1- and C3-Allenylic Alkylation of Indoles

Zha，Taochun1; Rui，Jiehui1; Zhang，Zhihan2; Zhang，Dongqiang1; Yang，Zhirong1; Yu，Peiyuan2; Wang，Yingcheng1; Peng，Fangzhi1; Shao，Zhihui1

2023-05-15

10.1002/anie.202300844

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

Herein we report a Pd-catalyzed asymmetric allenylic alkylation strategy for the direct functionalization of 1H-indoles by employing P-chiral BIBOP-type ligands. The regioselectivity (N1/C3) of this process can be switched efficiently. Using CsCO at elevated temperatures in MeCN, N1-alkylated indoles bearing axial chirality with a stereocenter non-adjacent (β) to the nitrogen are produced in good yields with high enantioselectivity and complete N1-regioselectivity regardless of the electronic properties and substitution patterns of diverse indoles. Using KCO at room temperature in CHCl, chiral C3-alkylated indoles can also be obtained. Notably, we introduce a new class of tri-substituted allenylic electrophiles that proceeded through different pathways from di-substituted allenylic electrophiles.

Allenylic Alkylation Asymmetric Synthesis Indoles Kinetic Resolution Regiodivergence

SCI ; EI

英语

NI论文

通讯

National Natural Science Foundation of China["22171240","22001229","21861042"] ; Program for Changjiang Scholars and Innovative Research Team in University[IRT17R94] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000970649200001

WILEY-V C H VERLAG GMBH

20231613902539

Cesium compounds ; Chlorine compounds ; Electronic properties ; Potash ; Regioselectivity

Chemical Reactions:802.2 ; Inorganic Compounds:804.2

CHEMISTRY

2-s2.0-85152527384

Scopus

1.Key Laboratory of Medicinal Chemistry for Natural Resource,Ministry of Education,School of Chemical Science and Technology,Yunnan Provincial Center for Research & Development of Natural Products,State Key Laboratory for Conservation and Utilization of Bio-Resources in Yunnan,Yunnan University,Kunming,650091,China
2.Department of Chemistry and Shenzhen Grubbs Institute,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China

Zha，Taochun,Rui，Jiehui,Zhang，Zhihan,et al. Direct Catalytic Asymmetric and Regiodivergent N1- and C3-Allenylic Alkylation of Indoles[J]. Angewandte Chemie - International Edition,2023,62(21).

Zha，Taochun.,Rui，Jiehui.,Zhang，Zhihan.,Zhang，Dongqiang.,Yang，Zhirong.,...&Shao，Zhihui.(2023).Direct Catalytic Asymmetric and Regiodivergent N1- and C3-Allenylic Alkylation of Indoles.Angewandte Chemie - International Edition,62(21).

Zha，Taochun,et al."Direct Catalytic Asymmetric and Regiodivergent N1- and C3-Allenylic Alkylation of Indoles".Angewandte Chemie - International Edition 62.21(2023).