Successive carbon-carbon bond formation by sequential generation of radical and anionic species with manganese and catalytic amounts of PbCl2 and Me3SiCl

Kazuhiko Takai, Takashi Ueda, Norihiko Ikeda, Takaya Ishiyama, Hiroshi Matsushita

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Three-component coupling reactions of iodoalkanes, α,β-unsaturated nitriles (or esters), and carbonyl compounds are achieved in good to excellent yields with a moderate reducing system derived from manganese metal and a catalytic amount of PbCl2 and Me3SiCl. Although the role of PbCl2 is unclear, addition of a catalytic amount of the salt is essential for reducing the iodoalkane. The reaction proceeds with primary, secondary, and tertiary iodoalkanes. Both acrylonitrile and acrylic esters can be employed as activated olefins, while the reaction with an alkyl vinyl ketone gives a complex mixture. Ketones and aldehydes can be used as the third component and the diastereoselectivity of the anionic addition is approximately 1: 1-2: 1 ratio. By using the heterogenerative process, i.e., successive 1,4-addition by radical and anionic internal addition, cyclopropanation of electron- deficient olefins is achieved with chloroiodomethane, manganese, PbCl2, Me3SiCl, and DMAP.

Original languageEnglish
Pages (from-to)347-353
Number of pages7
JournalBulletin of the Chemical Society of Japan
Volume76
Issue number2
DOIs
Publication statusPublished - 2003

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Manganese
Carbon
Alkenes
Ketones
Esters
Acrylonitrile
Carbonyl compounds
Nitriles
Complex Mixtures
Aldehydes
Acrylics
Salts
Metals
Electrons
lead chloride

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Successive carbon-carbon bond formation by sequential generation of radical and anionic species with manganese and catalytic amounts of PbCl2 and Me3SiCl. / Takai, Kazuhiko; Ueda, Takashi; Ikeda, Norihiko; Ishiyama, Takaya; Matsushita, Hiroshi.

In: Bulletin of the Chemical Society of Japan, Vol. 76, No. 2, 2003, p. 347-353.

Research output: Contribution to journalArticle

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