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

Escuela Nacional de Ciencias Biológicas (ENCB)

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

12 Scopus citations

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
State	Published - 1996

Keywords

Acetylvinyl carboxylates
Captodative
Catalysis
Diels-alder
Lewis acids
Stereoselectivity

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@article{8f58a1e1e9b346be9d2722653effa4b2,

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 = "Ingl{\'e}s",

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

UR - http://www.scopus.com/inward/record.url?scp=1342276172&partnerID=8YFLogxK

M3 - Artículo

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

Keywords

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