Facilitating the transmetalation step with aryl-zincates in nickel-catalyzed enantioselective arylation of secondary benzylic halides

被引:49
|
作者
Huang, Weichen [1 ]
Hu, Mei [2 ]
Wan, Xiaolong [1 ]
Shen, Qilong [1 ]
机构
[1] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Organofluorine Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China
[2] Univ Jinan, Shandong Engn Res Ctr Fluorinated Mat, Sch Chem & Chem Engn, Shandong Prov Key Lab Fluorine Chem & Chem Mat, Jinan 250022, Shandong, Peoples R China
基金
中国国家自然科学基金;
关键词
SUZUKI CROSS-COUPLINGS; ALKYL ELECTROPHILES; ASYMMETRIC FLUORINATION; NEGISHI REACTIONS; TRIFLUOROMETHYLATION; BROMIDES;
D O I
10.1038/s41467-019-10851-4
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Nickel-catalyzed asymmetric cross-coupling of secondary alkyl electrophiles with different nucleophiles represents a powerful strategy for the construction of chiral tertiary carbon centers. Yet, the use of aryl Grignard reagents or aryl zinc halides in many reactions typically resulted in low enantioselectivity, mainly due to their slow transmetalation step in the catalytical cycle and consequently the requirement of relatively high temperature. Here we report that the use of lithium aryl zincate [Ph2ZnBr]Li facilitates the transmetalation step of the nickel-catalyzed cross-coupling reaction. Based on this discovery, a highly enantioselective construction of fluoroalkyl-substituted stereogenic center by a nickel-catalyzed asymmetric Suzuki-Miyaura coupling of alpha-bromobenzyl trifluoro-/difluoro-/mono- fluoromethanes with a variety of lithium aryl zincates [Ph2ZnBr]Li that were in situ generated from the reaction of lithium orgaoboronate with 1.0 equivalent of ZnBr2 was described.
引用
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页数:8
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