Vinyl polymerization versus [1,3] O to C rearrangement in the ruthenium-catalyzed reactions of vinyl ethers with hydrosilanes

Nari Aki Harada, Takashi Nishikata, Hideo Nagashima

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Two reactions, vinyl polymerization and [1,3] O to C rearrangement of vinyl ethers, are investigated in the ruthenium-catalyzed reaction with hydrosilanes. The reaction pathways are dependent on the substituents of the vinyl ether, in particular, those of the alkoxy group. Primary-, secondary-, and tertiary-alkyl vinyl ethers, ROCHCH 2, are polymerized with ease to give the corresponding polymer in good yields. When R is electron-donating benzyl groups, the reaction does not give the polyvinyl ether but results in [1,3] O to C rearrangement to give the corresponding aldehyde, RCH 2CHO in moderate to good yields. The rearrangement selectively proceeds when vinyl ethers having α-substituents are used as the starting materials to give the corresponding ketones in high yields. With catalytic amounts of hydrosilanes, the rearrangement gives ketones or aldehydes selectively. In sharp contrast, use of excess amounts of hydrosilanes leads to the rearrangement followed by reduction of the formed carbonyl group to give the corresponding silyl ethers in good yields. Nature of catalytically active species is discussed. Crown

Original languageEnglish
Pages (from-to)3243-3252
Number of pages10
JournalTetrahedron
Volume68
Issue number15
DOIs
Publication statusPublished - Apr 15 2012

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Ruthenium
Polymerization
Ketones
Aldehydes
Polyvinyls
Ethers
Crowns
Ether
Polymers
Electrons
vinyl ether

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Vinyl polymerization versus [1,3] O to C rearrangement in the ruthenium-catalyzed reactions of vinyl ethers with hydrosilanes. / Harada, Nari Aki; Nishikata, Takashi; Nagashima, Hideo.

In: Tetrahedron, Vol. 68, No. 15, 15.04.2012, p. 3243-3252.

Research output: Contribution to journalArticle

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AB - Two reactions, vinyl polymerization and [1,3] O to C rearrangement of vinyl ethers, are investigated in the ruthenium-catalyzed reaction with hydrosilanes. The reaction pathways are dependent on the substituents of the vinyl ether, in particular, those of the alkoxy group. Primary-, secondary-, and tertiary-alkyl vinyl ethers, ROCHCH 2, are polymerized with ease to give the corresponding polymer in good yields. When R is electron-donating benzyl groups, the reaction does not give the polyvinyl ether but results in [1,3] O to C rearrangement to give the corresponding aldehyde, RCH 2CHO in moderate to good yields. The rearrangement selectively proceeds when vinyl ethers having α-substituents are used as the starting materials to give the corresponding ketones in high yields. With catalytic amounts of hydrosilanes, the rearrangement gives ketones or aldehydes selectively. In sharp contrast, use of excess amounts of hydrosilanes leads to the rearrangement followed by reduction of the formed carbonyl group to give the corresponding silyl ethers in good yields. Nature of catalytically active species is discussed. Crown

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