Allylic stereocontrol of the intramolecular diels-alder reaction

Michael J. Lilly; Natalie A. Miller; Alison J. Edwards; Anthony C. Willis; Peter Turner; Michael N. Paddon-Row; Michael S. Sherburn

doi:10.1002/chem.200401215

Allylic stereocontrol of the intramolecular diels-alder reaction

Michael J. Lilly, Natalie A. Miller, Alison J. Edwards, Anthony C. Willis, Peter Turner, Michael N. Paddon-Row^*, Michael S. Sherburn

^*Corresponding author for this work

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

25 Citations (Scopus)

Abstract

The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituants about a stereogenic center attached to Cl. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dieno phile. The stereochemical outcomes of these reactions are explained by reference to B3LYP/6-31G(d) transition structures. New insights into the conformational preferences of allylic alcohol derivatives are reported, results which allow an explanation of the differing levels of π-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.

Original language	English
Pages (from-to)	2525-2536
Number of pages	12
Journal	Chemistry - A European Journal
Volume	11
Issue number	8
DOIs	https://doi.org/10.1002/chem.200401215
Publication status	Published - 8 Apr 2005

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abstract = "The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituants about a stereogenic center attached to Cl. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dieno phile. The stereochemical outcomes of these reactions are explained by reference to B3LYP/6-31G(d) transition structures. New insights into the conformational preferences of allylic alcohol derivatives are reported, results which allow an explanation of the differing levels of π-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.",

keywords = "Chiral pool, Cyclo-addition, Density functional calculations, Diastereoselectivity, Synthetic methods",

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T1 - Allylic stereocontrol of the intramolecular diels-alder reaction

AU - Lilly, Michael J.

AU - Miller, Natalie A.

AU - Edwards, Alison J.

AU - Willis, Anthony C.

AU - Turner, Peter

AU - Paddon-Row, Michael N.

AU - Sherburn, Michael S.

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AB - The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituants about a stereogenic center attached to Cl. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dieno phile. The stereochemical outcomes of these reactions are explained by reference to B3LYP/6-31G(d) transition structures. New insights into the conformational preferences of allylic alcohol derivatives are reported, results which allow an explanation of the differing levels of π-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.

KW - Chiral pool

KW - Cyclo-addition

KW - Density functional calculations

KW - Diastereoselectivity

KW - Synthetic methods

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U2 - 10.1002/chem.200401215

DO - 10.1002/chem.200401215

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 8

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Allylic stereocontrol of the intramolecular diels-alder reaction

Abstract

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