Sequence-Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones

被引：90

作者：

Liu, Xi-Jia ^{[1
]}

Jin, Shicheng ^{[1
]}

Zhang, Wen-Yun ^{[1
]}

Liu, Qiang-Qiang ^{[1
]}

Zheng, Chao ^{[1
]}

You, Shu-Li ^{[1
]}

机构：

[1] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem,Ctr Excellence Mo, 345 Lingling Lu, Shanghai 200032, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 05期

关键词：

allylic alkylation; asymmetric catalysis; fluorination; iridium; stereodivergent synthesis; PD-CATALYZED ALLYLATION; ALPHA-AMINO-ACIDS; DUAL CATALYSIS; DECARBOXYLATIVE ALLYLATION; ENANTIOSELECTIVE SYNTHESIS; QUATERNARY STEREOCENTERS; SYNERGISTIC IRIDIUM; HIGHLY REGIO; ALKYLATION; DIASTEREO;

D O I：

10.1002/anie.201912882

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The stereodivergent iridium-catalyzed allylic alkylation and fluorination of acyclic ketones is described. alpha-Pyridyl-alpha-fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities. Distinct from known stereodivergent synthesis, for which two different chiral catalysts are required in general, herein we report a sequence-dependent stereodivergent synthesis. With only a single chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.

引用

页码：2039 / 2043

页数：5

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