Diels-Alder reaction of dienes having stereogenic allylic substituents:  control of diastereoface selectivity by the dienophile

Tripathy, Rabindranath; Franck, Richard W.; Onan, Kay D.

doi:10.1021/ja00218a041

Cited by 100 publications

(34 citation statements)

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“…Evidence presented for this sequence of events centred on observations of a gradual improvement in p-diastereofacial selectivity with progressively larger silyl ether derivatives of chiral dienols. 8 Perhaps the most convincing support for the IMDA route in Scheme 1 is the exclusive formation of cis-fused lactone acids from pre-formed half ester derivatives of substituted maleic anhydrides. 10-14 Thus, White and Sheldon 10, 11 reported that heating a 50 : 50 mixture of citraconate half esters 9 and 10 in xylene at reflux produces a single crystalline product 11 in low yield along with a substantial quantity of polymer † Electronic supplementary information (ESI) available: synthetic procedures, characterisation details, selected time lapse 1 (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

On the Diels–Alder reactions of pentadienyl maleates and citraconates

et al. 2005

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Reactions between conjugated dienols and maleic anhydride provide either cis-fused or trans-fused bicyclic products as major products, depending upon how the reaction is carried out. Simply mixing the two reactants together generally leads to cis-fused lactone acids in thermal reactions which proceed viaintermolecular Diels-Alder reaction followed by intramolecular esterification. Pre-forming the maleate half ester derivative followed by heating affords predominantly trans-fused lactone acids in good yields by way of an intramolecular Diels-Alder (IMDA) reaction. Sorbyl citraconate half esters undergo a rapid thermolytic fragmentation in refluxing toluene to form the dienol and citraconic anhydride. The resulting diene-dienophile pair undergo an intermolecular cycloaddition followed by a rapid intramolecular esterification to give cis-fused bicyclic lactone acids as major products. The IMDA reaction of citraconic half esters is sufficiently rapid in DMSO to dominate over fragmentation: the exo-cycloadduct is formed almost exclusively. Nine literature reports of endo-selective IMDA reactions of triene acids are erroneous; the cycloadditions proceed in an intermolecular manner.

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Section: Introductionmentioning

confidence: 99%

On the Diels–Alder reactions of pentadienyl maleates and citraconates

et al. 2005

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“…), as expected for maleimide dienophiles. 21 Access to these functionalized dienes traditionally requires differentiation of bifunctional starting materials using lengthy protecting group manipulation sequences. Alternatively, this dehydrogenation manifold provides direct access to 1,3-diene intermediates from mono-functional terminal olefins, the majority of which are generated in one step from commercial starting materials.…”

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confidence: 99%

Molecular Complexity via C–H Activation: A Dehydrogenative Diels–Alder Reaction

2011

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Traditionally, C–H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C–H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation.

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“…The dienophile reacts at the more accessible π‐face of the diene; in the absence of overriding electronic effects, this will be on the side of the diene in which the smaller substituent resides. This model, which also explains the outcomes of inter molecular Diels–Alder reactions of acyclic chiral dienols and derivatives,29b, c is being further explored and tested.…”

Section: Closing Remarksmentioning

confidence: 99%

Allylic Stereocontrol of the Intramolecular Diels–Alder Reaction

Lilly¹,

Miller²,

Edwards³

et al. 2005

Chemistry A European J

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The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituents about a stereogenic center attached to C1. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dienophile. The stereochemical outcomes of these reactions are explained by reference to B3 LYP/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 pi-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.

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Diels-Alder reaction of dienes having stereogenic allylic substituents: control of diastereoface selectivity by the dienophile

Cited by 100 publications

References 0 publications

On the Diels–Alder reactions of pentadienyl maleates and citraconates

On the Diels–Alder reactions of pentadienyl maleates and citraconates

Molecular Complexity via C–H Activation: A Dehydrogenative Diels–Alder Reaction

Allylic Stereocontrol of the Intramolecular Diels–Alder Reaction

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