W(CO)5(L)-catalyzed 6-endo-selective cyclization and formal Cope rearrangement of allenyl silyl enol ethers

Tomoya Miura; Koichi Kiyota; Hiroyuki Kusama; Nobuharu Iwasawa

doi:10.1016/j.jorganchem.2006.08.037

W(CO)₅(L)-catalyzed 6-endo-selective cyclization and formal Cope rearrangement of allenyl silyl enol ethers

Tomoya Miura, Koichi Kiyota, Hiroyuki Kusama, Nobuharu Iwasawa

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

2 Citations (Scopus)

Abstract

On treatment of 5-siloxy-1,2,5-trienes with a catalytic amount of W(CO)₆ under photoirradiation, two types of synthetically useful compounds, that is, 6-endo-cyclized products or formal Cope rearrangement products, are obtained selectively via the same intermediates simply by changing reaction conditions. In these reactions, electrophilic activation of the allene moiety is effectively achieved by coordination of W(CO)₅, allowing intramolecular attack by neutral carbon nucleophiles in a 6-endo manner.

Original language	English
Pages (from-to)	562-568
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	692
Issue number	1-3
DOIs	https://doi.org/10.1016/j.jorganchem.2006.08.037
Publication status	Published - Jan 1 2007
Externally published	Yes

Keywords

Allene
Cope rearrangement
Cyclization
Electrophilic activation
Tungsten

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jorganchem.2006.08.037

Cite this

@article{09bea7ad0489489a8aba965ac30044af,

title = "W(CO)5(L)-catalyzed 6-endo-selective cyclization and formal Cope rearrangement of allenyl silyl enol ethers",

abstract = "On treatment of 5-siloxy-1,2,5-trienes with a catalytic amount of W(CO)6 under photoirradiation, two types of synthetically useful compounds, that is, 6-endo-cyclized products or formal Cope rearrangement products, are obtained selectively via the same intermediates simply by changing reaction conditions. In these reactions, electrophilic activation of the allene moiety is effectively achieved by coordination of W(CO)5, allowing intramolecular attack by neutral carbon nucleophiles in a 6-endo manner.",

keywords = "Allene, Cope rearrangement, Cyclization, Electrophilic activation, Tungsten",

author = "Tomoya Miura and Koichi Kiyota and Hiroyuki Kusama and Nobuharu Iwasawa",

note = "Funding Information: This work was supported by Grant-in-Aid for Scientific Research on Priority Area “Reaction Control of Dynamic Complexes” from Ministry of Education, Culture, Sports, Science, and Technology, Japan. T.M. was granted a Research Fellowship of the Japan Society for the Promotion of Science for Young Scientists.",

year = "2007",

month = jan,

day = "1",

doi = "10.1016/j.jorganchem.2006.08.037",

language = "English",

volume = "692",

pages = "562--568",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-3",

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TY - JOUR

T1 - W(CO)5(L)-catalyzed 6-endo-selective cyclization and formal Cope rearrangement of allenyl silyl enol ethers

AU - Miura, Tomoya

AU - Kiyota, Koichi

AU - Kusama, Hiroyuki

AU - Iwasawa, Nobuharu

N1 - Funding Information: This work was supported by Grant-in-Aid for Scientific Research on Priority Area “Reaction Control of Dynamic Complexes” from Ministry of Education, Culture, Sports, Science, and Technology, Japan. T.M. was granted a Research Fellowship of the Japan Society for the Promotion of Science for Young Scientists.

PY - 2007/1/1

Y1 - 2007/1/1

N2 - On treatment of 5-siloxy-1,2,5-trienes with a catalytic amount of W(CO)6 under photoirradiation, two types of synthetically useful compounds, that is, 6-endo-cyclized products or formal Cope rearrangement products, are obtained selectively via the same intermediates simply by changing reaction conditions. In these reactions, electrophilic activation of the allene moiety is effectively achieved by coordination of W(CO)5, allowing intramolecular attack by neutral carbon nucleophiles in a 6-endo manner.

AB - On treatment of 5-siloxy-1,2,5-trienes with a catalytic amount of W(CO)6 under photoirradiation, two types of synthetically useful compounds, that is, 6-endo-cyclized products or formal Cope rearrangement products, are obtained selectively via the same intermediates simply by changing reaction conditions. In these reactions, electrophilic activation of the allene moiety is effectively achieved by coordination of W(CO)5, allowing intramolecular attack by neutral carbon nucleophiles in a 6-endo manner.

KW - Allene

KW - Cope rearrangement

KW - Cyclization

KW - Electrophilic activation

KW - Tungsten

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U2 - 10.1016/j.jorganchem.2006.08.037

DO - 10.1016/j.jorganchem.2006.08.037

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AN - SCOPUS:33845650734

SN - 0022-328X

VL - 692

SP - 562

EP - 568

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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