Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane

Cristóbal Rodríguez-García; Javier Ibarzo; Ángel Álvarez-Larena; Vicenç Branchadell; Antoni Oliva; Rosa M. Ortuño

doi:10.1016/S0040-4020(00)01061-9

Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane

Cristóbal Rodríguez-García, Javier Ibarzo, Ángel Álvarez-Larena, Vicenç Branchadell, Antoni Oliva, Rosa M. Ortuño

Department of Chemistry

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

18 Citations (Scopus)

Abstract

Several chiral polyfunctionalyzed cyclohexanones and cyclohexenones have been synthesized through Diels-Alder cycloadditions, stereoselectivity being stated by X-ray structural analysis and NOE experiments. The chemoselectivity in the palladium(II)-catalyzed reaction between cyclohexenones and diazomethane has been investigated. Thus, in those enones bearing an amide function on the γ-carbon, the preferential addition occurs at the carbonyl giving epoxides which, under acid conditions, rearrange to tetrahydrobenzoxazoles. The other cyclohexenones afford cyclopropanes as a result of addition to the C=C bond. A mechanistic approach to explain the whole process is proposed. © 2001 Elsevier Science Ltd.

Original language	English
Pages (from-to)	1025-1034
Journal	Tetrahedron
Volume	57
Issue number	6
DOIs	https://doi.org/10.1016/S0040-4020(00)01061-9
Publication status	Published - 4 Feb 2001

Keywords

Benzoxazole
Chemoselectivity
Cyclohexanones
Cyclohexenones
Cyclopropanatio n
Diazomethane
Diels-Alder reactions
Oxiranes
Palladium diacetate

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10.1016/S0040-4020(00)01061-9

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title = "Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane",

abstract = "Several chiral polyfunctionalyzed cyclohexanones and cyclohexenones have been synthesized through Diels-Alder cycloadditions, stereoselectivity being stated by X-ray structural analysis and NOE experiments. The chemoselectivity in the palladium(II)-catalyzed reaction between cyclohexenones and diazomethane has been investigated. Thus, in those enones bearing an amide function on the γ-carbon, the preferential addition occurs at the carbonyl giving epoxides which, under acid conditions, rearrange to tetrahydrobenzoxazoles. The other cyclohexenones afford cyclopropanes as a result of addition to the C=C bond. A mechanistic approach to explain the whole process is proposed. {\textcopyright} 2001 Elsevier Science Ltd.",

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author = "Crist{\'o}bal Rodr{\'i}guez-Garc{\'i}a and Javier Ibarzo and {\'A}ngel {\'A}lvarez-Larena and Vicen{\c c} Branchadell and Antoni Oliva and Ortu{\~n}o, {Rosa M.}",

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doi = "10.1016/S0040-4020(00)01061-9",

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Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane. / Rodríguez-García, Cristóbal; Ibarzo, Javier; Álvarez-Larena, Ángel; Branchadell, Vicenç; Oliva, Antoni; Ortuño, Rosa M.

In: Tetrahedron, Vol. 57, No. 6, 04.02.2001, p. 1025-1034.

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

TY - JOUR

T1 - Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane

AU - Rodríguez-García, Cristóbal

AU - Ibarzo, Javier

AU - Álvarez-Larena, Ángel

AU - Branchadell, Vicenç

AU - Oliva, Antoni

AU - Ortuño, Rosa M.

PY - 2001/2/4

Y1 - 2001/2/4

N2 - Several chiral polyfunctionalyzed cyclohexanones and cyclohexenones have been synthesized through Diels-Alder cycloadditions, stereoselectivity being stated by X-ray structural analysis and NOE experiments. The chemoselectivity in the palladium(II)-catalyzed reaction between cyclohexenones and diazomethane has been investigated. Thus, in those enones bearing an amide function on the γ-carbon, the preferential addition occurs at the carbonyl giving epoxides which, under acid conditions, rearrange to tetrahydrobenzoxazoles. The other cyclohexenones afford cyclopropanes as a result of addition to the C=C bond. A mechanistic approach to explain the whole process is proposed. © 2001 Elsevier Science Ltd.

AB - Several chiral polyfunctionalyzed cyclohexanones and cyclohexenones have been synthesized through Diels-Alder cycloadditions, stereoselectivity being stated by X-ray structural analysis and NOE experiments. The chemoselectivity in the palladium(II)-catalyzed reaction between cyclohexenones and diazomethane has been investigated. Thus, in those enones bearing an amide function on the γ-carbon, the preferential addition occurs at the carbonyl giving epoxides which, under acid conditions, rearrange to tetrahydrobenzoxazoles. The other cyclohexenones afford cyclopropanes as a result of addition to the C=C bond. A mechanistic approach to explain the whole process is proposed. © 2001 Elsevier Science Ltd.

KW - Benzoxazole

KW - Chemoselectivity

KW - Cyclohexanones

KW - Cyclohexenones

KW - Cyclopropanatio n

KW - Diazomethane

KW - Diels-Alder reactions

KW - Oxiranes

KW - Palladium diacetate

U2 - 10.1016/S0040-4020(00)01061-9

DO - 10.1016/S0040-4020(00)01061-9

M3 - Article

VL - 57

SP - 1025

EP - 1034

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 6

ER -

Stereoselective synthesis of chiral polyfunctionalized cyclohexane derivatives. Palladium(II)-mediated reaction between cyclohexenones and diazomethane

Abstract

Keywords

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