Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes

Sobi Asako, Sae Ishikawa, Kazuhiko Takai

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A simple molybdenum-based catalytic system for hydrosilylation of allenes has been developed. The reactions of mono- and disubstituted allenes with secondary and tertiary silanes proceeded smoothly and selectively to afford linear allylsilanes. The origin of the unprecedented linear selectivity was investigated by density functional theory studies to reveal that the reaction consists of the following steps: (1) concerted hydromolybdation/Si-H oxidative addition from a Mo(CO)4/allene/silane adduct to form (π-allyl)molybdenum, (2) allyl rotation from the initially formed (π-allyl)molybdenum to a thermodynamically more stable isomer, and (3) reductive elimination at the less-hindered allyl carbon to afford a linear allylsilane.

Original languageEnglish
Pages (from-to)3387-3395
Number of pages9
JournalACS Catalysis
Volume6
Issue number5
DOIs
Publication statusPublished - May 6 2016

Fingerprint

Hydrosilylation
Molybdenum
Silanes
Carbon Monoxide
Isomers
Density functional theory
Carbon
allylsilane
propadiene

Keywords

  • allenes
  • allyl rotation
  • density functional theory
  • hydrosilylation
  • linear allylsilanes
  • molybdenum

ASJC Scopus subject areas

  • Catalysis

Cite this

Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes. / Asako, Sobi; Ishikawa, Sae; Takai, Kazuhiko.

In: ACS Catalysis, Vol. 6, No. 5, 06.05.2016, p. 3387-3395.

Research output: Contribution to journalArticle

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N2 - A simple molybdenum-based catalytic system for hydrosilylation of allenes has been developed. The reactions of mono- and disubstituted allenes with secondary and tertiary silanes proceeded smoothly and selectively to afford linear allylsilanes. The origin of the unprecedented linear selectivity was investigated by density functional theory studies to reveal that the reaction consists of the following steps: (1) concerted hydromolybdation/Si-H oxidative addition from a Mo(CO)4/allene/silane adduct to form (π-allyl)molybdenum, (2) allyl rotation from the initially formed (π-allyl)molybdenum to a thermodynamically more stable isomer, and (3) reductive elimination at the less-hindered allyl carbon to afford a linear allylsilane.

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