Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes

Tory Cayzer; Michael Paddon-Row; Damian Moran; Alan Payne; Mick Sherburn; Peter Turner

doi:10.1021/jo0505829

Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes

Tory Cayzer, Michael Paddon-Row, Damian Moran, Alan Payne, Mick Sherburn, Peter Turner

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

Abstract

Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels-Alder (IMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene C1 substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.

Original language	English
Pages (from-to)	5561-5570
Journal	Journal of Organic Chemistry
Volume	70
Issue number	14
DOIs	https://doi.org/10.1021/jo0505829
Publication status	Published - 2005

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title = "Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes",

abstract = "Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels-Alder (IMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene C1 substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.",

author = "Tory Cayzer and Michael Paddon-Row and Damian Moran and Alan Payne and Mick Sherburn and Peter Turner",

year = "2005",

doi = "10.1021/jo0505829",

language = "English",

volume = "70",

pages = "5561--5570",

journal = "Journal of Organic Chemistry",

publisher = "American Chemical Society",

number = "14",

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TY - JOUR

T1 - Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes

AU - Cayzer, Tory

AU - Paddon-Row, Michael

AU - Moran, Damian

AU - Payne, Alan

AU - Sherburn, Mick

AU - Turner, Peter

PY - 2005

Y1 - 2005

N2 - Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels-Alder (IMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene C1 substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.

AB - Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels-Alder (IMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene C1 substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.

U2 - 10.1021/jo0505829

DO - 10.1021/jo0505829

M3 - Article

VL - 70

SP - 5561

EP - 5570

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 14

ER -

Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes

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