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

Sobi Asako; Sae Ishikawa; Kazuhiko Takai

doi:10.1021/acscatal.6b00627

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

Sobi Asako, Sae Ishikawa, Kazuhiko Takai

Research output: Contribution to journal › Article › peer-review

30 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 language	English
Pages (from-to)	3387-3395
Number of pages	9
Journal	ACS Catalysis
Volume	6
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.6b00627
Publication status	Published - May 6 2016

Keywords

allenes
allyl rotation
density functional theory
hydrosilylation
linear allylsilanes
molybdenum

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1021/acscatal.6b00627

Cite this

@article{eddfbdf8f8564c37b3a94ecd59436915,

title = "Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes",

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.",

keywords = "allenes, allyl rotation, density functional theory, hydrosilylation, linear allylsilanes, molybdenum",

author = "Sobi Asako and Sae Ishikawa and Kazuhiko Takai",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = may,

day = "6",

doi = "10.1021/acscatal.6b00627",

language = "English",

volume = "6",

pages = "3387--3395",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes

AU - Asako, Sobi

AU - Ishikawa, Sae

AU - Takai, Kazuhiko

PY - 2016/5/6

Y1 - 2016/5/6

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.

AB - 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.

KW - allenes

KW - allyl rotation

KW - density functional theory

KW - hydrosilylation

KW - linear allylsilanes

KW - molybdenum

UR - http://www.scopus.com/inward/record.url?scp=84973525534&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84973525534&partnerID=8YFLogxK

U2 - 10.1021/acscatal.6b00627

DO - 10.1021/acscatal.6b00627

M3 - Article

AN - SCOPUS:84973525534

SN - 2155-5435

VL - 6

SP - 3387

EP - 3395

JO - ACS Catalysis

JF - ACS Catalysis

IS - 5

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this