Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes

Kazusa Ota, Ick Lee Sang, Jhih Meng Tang, Manabu Takachi, Hiromi Nakai, Tsumoru Morimoto, Hitoshi Sakurai, Ken Kataoka, Naoto Chatani

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.

Original languageEnglish
Pages (from-to)15203-15211
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number42
DOIs
Publication statusPublished - 2009 Oct 28
Externally publishedYes

Fingerprint

Alkynes
Carbon
Chemical activation
Derivatives
Rhodium
Alkenes
Cyclization
Phenol
Isomers
Olefins
Phenols
Catalyst activity
Substitution reactions
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes. / Ota, Kazusa; Sang, Ick Lee; Tang, Jhih Meng; Takachi, Manabu; Nakai, Hiromi; Morimoto, Tsumoru; Sakurai, Hitoshi; Kataoka, Ken; Chatani, Naoto.

In: Journal of the American Chemical Society, Vol. 131, No. 42, 28.10.2009, p. 15203-15211.

Research output: Contribution to journalArticle

Ota, K, Sang, IL, Tang, JM, Takachi, M, Nakai, H, Morimoto, T, Sakurai, H, Kataoka, K & Chatani, N 2009, 'Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes', Journal of the American Chemical Society, vol. 131, no. 42, pp. 15203-15211. https://doi.org/10.1021/ja9047637
Ota, Kazusa ; Sang, Ick Lee ; Tang, Jhih Meng ; Takachi, Manabu ; Nakai, Hiromi ; Morimoto, Tsumoru ; Sakurai, Hitoshi ; Kataoka, Ken ; Chatani, Naoto. / Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 42. pp. 15203-15211.
@article{aa7dd0433bb84d6dab7a3b6bdf6e89b3,
title = "Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes",
abstract = "The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.",
author = "Kazusa Ota and Sang, {Ick Lee} and Tang, {Jhih Meng} and Manabu Takachi and Hiromi Nakai and Tsumoru Morimoto and Hitoshi Sakurai and Ken Kataoka and Naoto Chatani",
year = "2009",
month = "10",
day = "28",
doi = "10.1021/ja9047637",
language = "English",
volume = "131",
pages = "15203--15211",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "42",

}

TY - JOUR

T1 - Rh(II)-catalyzed skeletal reorganization of 1,6- and 1,7-enynes through electrophilic activation of alkynes

AU - Ota, Kazusa

AU - Sang, Ick Lee

AU - Tang, Jhih Meng

AU - Takachi, Manabu

AU - Nakai, Hiromi

AU - Morimoto, Tsumoru

AU - Sakurai, Hitoshi

AU - Kataoka, Ken

AU - Chatani, Naoto

PY - 2009/10/28

Y1 - 2009/10/28

N2 - The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.

AB - The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(II) as a catalyst is reported. Two possible isomers of 1-vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(II) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.

UR - http://www.scopus.com/inward/record.url?scp=70350660550&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70350660550&partnerID=8YFLogxK

U2 - 10.1021/ja9047637

DO - 10.1021/ja9047637

M3 - Article

C2 - 19807073

AN - SCOPUS:70350660550

VL - 131

SP - 15203

EP - 15211

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 42

ER -