Rhodium-Catalyzed Atroposelective [2+2+2] Cycloaddition of Ortho-Substituted Phenyl Diynes with Nitriles: Effect of Ortho Substituents on Regio- and Enantioselectivity

被引：47

作者：

Kashima, Kenichi ^{[1
,3
]}

Teraoka, Kota ^{[2
]}

Uekusa, Hidehiro ^{[2
]}

Shibata, Yu ^{[1
]}

Tanaka, Ken ^{[1
,3
]}

机构：

[1] Tokyo Inst Technol, Grad Sch Sci & Engn, Dept Appl Chem, Meguro Ku, Tokyo 1528550, Japan

[2] Tokyo Inst Technol, Grad Sch Sci & Engn, Dept Chem & Mat Sci, Meguro Ku, Tokyo 1528550, Japan

[3] Tokyo Univ Agr & Technol, Grad Sch Engn, Dept Appl Chem, Koganei, Tokyo 1848588, Japan

来源：

ORGANIC LETTERS | 2016年 / 18卷 / 09期

关键词：

AXIALLY CHIRAL BIARYLS; GASEOUS ALKYNE EQUIVALENTS; LIQUID ENOL ETHERS; CROSS-CYCLOTRIMERIZATION; ASYMMETRIC-SYNTHESIS; CONSTRUCTION; DERIVATIVES; PYRIDINES; ACETATES; HEXAYNES;

D O I：

10.1021/acs.orglett.6b00791

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Axially chiral 3-(2-halophenyl)pyridines were successfully synthesized in high yields with excellent enantioselectivity by the cationic rhodium(I)/(S)-H-8-BINAP complex-catalyzed atroposelective [2 + 2 + 2] cycloaddition of (o-halophenyl)diynes with nitriles. Interestingly, regio- and enantioselectivity highly depend on ortho substituents on the phenyl group of diynes. When the ortho substituents were methoxy and methoxycarbonyl groups, axially chiral 3-arylpyridines were obtained as a major product, while enantioselectivity was lowered significantly. On the other hand, when the ortho substituents were alkyl groups, regioselectivity was switched to give achiral 6-arylpyridines in high yields.

引用

页码：2170 / 2173

页数：4

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