Aldehydes as O-Nucleophiles in Cobalt Hydride Hydrogen Atom Transfer Catalysis: Overriding the Innate Somophilicity

被引：9

作者：

Nie, Yi-Chen ^{[1
]}

Yang, Fan ^{[1
]}

Li, Yu-Hao ^{[1
]}

Zhu, Rong ^{[1
]}

机构：

[1] Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Sci, Key Lab Bioorgan Chem & Mol Engn,Minist Educ, Beijing 100871, Peoples R China

来源：

ORGANIC LETTERS | 2023年

关键词：

INITIATED CYCLIZATIONS; UNACTIVATED OLEFINS; ALKENES; HYDROFUNCTIONALIZATION; HYDROALKOXYLATION; OXYGEN; FE;

D O I：

10.1021/acs.orglett.3c00131

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In metal hydride-catalyzed alkene hydrofunctional-ization reactions via hydrogen atom transfer, simple carbonyl groups have been well-recognized as good somophiles at the carbon for C-C bond formation. Here we report an alternative pathway exploring the carbonyl as an O-nucleophile to make new C-O bonds during the CoH-catalyzed oxidative cyclization of alkenyl aldehydes. This reaction provides a rapid, mild, modular, and stereoselective (up to >20:1) entry to saturated O-heterocycles via nucleophilic trapping of an in situ-formed oxocarbenium intermediate. The key to overriding the carbonyl's innate somophilicity was found to be promoting the formation of organocobalt species and suppressing the radical exchange.

引用

页码：889 / 894

页数：6

共 20 条

[1] Aldehydes as O-Nucleophiles in Cobalt Hydride Hydrogen Atom Transfer Catalysis: Overriding the Innate Somophilicity
Nie, Yi-Chen
Yang, Fan
Li, Yu-Hao
Zhu, Rong
ORGANIC LETTERS, 2023,
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