Desymmetrization as a Strategy in Asymmetric Halocyclization Reactions

Hennecke, Ulrich; Wilking, Michael

doi:10.1055/s-0033-1341160

Cited by 39 publications

(15 citation statements)

References 12 publications

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“…Indeed, catalytic asymmetric halogenation has attracted great interest over the last decade, because it enables simultaneous incorporation of two heteroatoms across unactivated alkenes . However, applications to asymmetric desymmetrization are still quite limited, even including stoichiometric variants with a chiral auxiliary, although we previously reported desymmetrization of 1,4‐cyclohexadiene acids by asymmetric bromolactonization with a commercially available cinchona alkaloid catalyst…”

Section: Methodsmentioning

confidence: 99%

Desymmetrization of Bisallylic Amides through Catalytic Enantioselective Bromocyclization with BINAP Monoxide

Nagao

Hisanaga

Egami

et al. 2017

Chemistry A European J

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We report the first desymmetrization of bisallylic amides by enantioselective bromocyclization with BINAP monoxide as a catalyst. Depending upon the substitution pattern of the alkene moieties, densely functionalized, optically active oxazoline or dihydrooxazine compounds were obtained in a highly stereoselective manner. The remaining alkene moiety was subjected to various functional group manipulations to afford a diverse array of chiral molecules with multiple stereogenic centers.

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Section: Methodsmentioning

confidence: 99%

Desymmetrization of Bisallylic Amides through Catalytic Enantioselective Bromocyclization with BINAP Monoxide

Nagao

Hisanaga

Egami

et al. 2017

Chemistry A European J

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“…However, other problems that needed to be solved involved desymmetrization of prochiral substrates and kinetic resolution of racemic substrates, although there have been several reports of alternative solutions since we completed our own work. 16 …”

Section: Resultsmentioning

confidence: 99%

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

et al. 2018

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A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4(Z)-olefinic acids via 5-exo mode cyclizations to give lactones in which new carbon–halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5(Z)-olefinic acids also occur via 6-exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.

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“…125 Desymmetrisation of bis-alkenoic acids through asymmetric protolactonisation was recently reported by K. Ishihara. Many of these are catalysed by acidic binaphthol derivatives that can form ion pairs with reactive haliranium intermediates.…”

Section: Alkenes Dienes and Diynesmentioning

confidence: 90%

Organocatalytic enantioselective desymmetrisation

et al. 2016

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Organocatalytic enantioselective desymmetrisation of achiral or meso compounds is a powerful strategy for the construction of enantiomerically enriched complex molecules, often with multiple stereocentres and in high selectivities. Recent years have seen increasing use of organocatalysts in desymmetrisation methodology, in contrast to traditional metal- or enzyme-catalysed reactions, with many impressive advances made in the current decade. This review will provide an overview of the field since 2010, with the aim of highlighting both the practical applications and elegance of enantioselective desymmetrisation to the wider synthetic community.

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Desymmetrization as a Strategy in Asymmetric Halocyclization Reactions

Cited by 39 publications

References 12 publications

Desymmetrization of Bisallylic Amides through Catalytic Enantioselective Bromocyclization with BINAP Monoxide

Desymmetrization of Bisallylic Amides through Catalytic Enantioselective Bromocyclization with BINAP Monoxide

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

Organocatalytic enantioselective desymmetrisation

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