Lewis acid-promoted stereoselective Diels-Alder cycloadditions of captodative olefins acetylvinyl carboxylates and NMR structural study of their cyclopentadiene adducts

Octavio García De Alba; Jorge Chanona; Francisco Delgado; Gerardo Zepeda; Fernando Labarrios; Roderick W. Bates; Simon Bott; Eusebio Juaristi; Joaquîn Tamariz

Lewis acid-promoted stereoselective Diels-Alder cycloadditions of captodative olefins acetylvinyl carboxylates and NMR structural study of their cyclopentadiene adducts

Octavio García De Alba^*, Jorge Chanona, Francisco Delgado, Gerardo Zepeda, Fernando Labarrios, Roderick W. Bates, Simon Bott, Eusebio Juaristi, Joaquîn Tamariz

^*Corresponding author for this work

Instituto Politécnico Nacional

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

12 Citations (Scopus)

Abstract

A study of Lewis acid-promoted Diels-Alder cycloadditions of the captodative olefins 1-acetyl vinyl carboxylates 1 with cyclopentadiene is described. Catalyst, temperature and solvent were the assessed variables, the exo/endo ratio being more significantly modified by the first one. Znh and TiCl4 showed the most remarkable effect with olefin la, giving very high and opposite stereoselectivity, since exo isomer 3 and endo 4 were the major adducts, respectively. The steric effect of the carboxylate substituent of 1 could participate in controlling the stereoselectivity. Structural characterization of the adducts was made by NMR and X-ray analysis. Electronic and anisotropic effects are probably involved in unusual proton chemical shifts of the norbornene structure of the adducts.

Original language	English
Pages (from-to)	108-117
Number of pages	10
Journal	Anales de Quimica
Volume	92
Issue number	2
Publication status	Published - 1996
Externally published	Yes

ASJC Scopus Subject Areas

General Chemistry

Keywords

Acetylvinyl carboxylates
Captodative
Catalysis
Diels-alder
Lewis acids
Stereoselectivity

Cite this

@article{1a33056e9ca0426a96f421e5a7b20a9e,

title = "Lewis acid-promoted stereoselective Diels-Alder cycloadditions of captodative olefins acetylvinyl carboxylates and NMR structural study of their cyclopentadiene adducts",

abstract = "A study of Lewis acid-promoted Diels-Alder cycloadditions of the captodative olefins 1-acetyl vinyl carboxylates 1 with cyclopentadiene is described. Catalyst, temperature and solvent were the assessed variables, the exo/endo ratio being more significantly modified by the first one. Znh and TiCl4 showed the most remarkable effect with olefin la, giving very high and opposite stereoselectivity, since exo isomer 3 and endo 4 were the major adducts, respectively. The steric effect of the carboxylate substituent of 1 could participate in controlling the stereoselectivity. Structural characterization of the adducts was made by NMR and X-ray analysis. Electronic and anisotropic effects are probably involved in unusual proton chemical shifts of the norbornene structure of the adducts.",

keywords = "Acetylvinyl carboxylates, Captodative, Catalysis, Diels-alder, Lewis acids, Stereoselectivity",

author = "{De Alba}, {Octavio Garc{\'i}a} and Jorge Chanona and Francisco Delgado and Gerardo Zepeda and Fernando Labarrios and Bates, {Roderick W.} and Simon Bott and Eusebio Juaristi and Joaqu{\^i}n Tamariz",

year = "1996",

language = "English",

volume = "92",

pages = "108--117",

journal = "Anales de Quimica",

issn = "1130-2283",

number = "2",

}

TY - JOUR

T1 - Lewis acid-promoted stereoselective Diels-Alder cycloadditions of captodative olefins acetylvinyl carboxylates and NMR structural study of their cyclopentadiene adducts

AU - De Alba, Octavio García

AU - Chanona, Jorge

AU - Delgado, Francisco

AU - Zepeda, Gerardo

AU - Labarrios, Fernando

AU - Bates, Roderick W.

AU - Bott, Simon

AU - Juaristi, Eusebio

AU - Tamariz, Joaquîn

PY - 1996

Y1 - 1996

N2 - A study of Lewis acid-promoted Diels-Alder cycloadditions of the captodative olefins 1-acetyl vinyl carboxylates 1 with cyclopentadiene is described. Catalyst, temperature and solvent were the assessed variables, the exo/endo ratio being more significantly modified by the first one. Znh and TiCl4 showed the most remarkable effect with olefin la, giving very high and opposite stereoselectivity, since exo isomer 3 and endo 4 were the major adducts, respectively. The steric effect of the carboxylate substituent of 1 could participate in controlling the stereoselectivity. Structural characterization of the adducts was made by NMR and X-ray analysis. Electronic and anisotropic effects are probably involved in unusual proton chemical shifts of the norbornene structure of the adducts.

AB - A study of Lewis acid-promoted Diels-Alder cycloadditions of the captodative olefins 1-acetyl vinyl carboxylates 1 with cyclopentadiene is described. Catalyst, temperature and solvent were the assessed variables, the exo/endo ratio being more significantly modified by the first one. Znh and TiCl4 showed the most remarkable effect with olefin la, giving very high and opposite stereoselectivity, since exo isomer 3 and endo 4 were the major adducts, respectively. The steric effect of the carboxylate substituent of 1 could participate in controlling the stereoselectivity. Structural characterization of the adducts was made by NMR and X-ray analysis. Electronic and anisotropic effects are probably involved in unusual proton chemical shifts of the norbornene structure of the adducts.

KW - Acetylvinyl carboxylates

KW - Captodative

KW - Catalysis

KW - Diels-alder

KW - Lewis acids

KW - Stereoselectivity

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M3 - Article

AN - SCOPUS:1342276172

SN - 1130-2283

VL - 92

SP - 108

EP - 117

JO - Anales de Quimica

JF - Anales de Quimica

IS - 2

ER -

Lewis acid-promoted stereoselective Diels-Alder cycloadditions of captodative olefins acetylvinyl carboxylates and NMR structural study of their cyclopentadiene adducts

Abstract

ASJC Scopus Subject Areas

Keywords

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