Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes

Volker Wedek; Ruben Van Lommel; Constantin G. Daniliuc; Frank De Proft; Ulrich Hennecke

doi:10.1002/anie.201901777

Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes

Volker Wedek, Ruben Van Lommel, Constantin G. Daniliuc, Frank De Proft, Ulrich Hennecke

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Abstract

The use of a new class of unsymmetrical cinchona-alkaloid-based, phthalazine-bridged organocatalysts enabled the highly enantioselective dichlorination of unfunctionalized alkenes. In combination with the electrophilic chlorinating agent 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and triethylsilyl chloride (TES-Cl) as the source of nucleophilic chloride, 1-aryl-2-alkyl alkenes were dichlorinated with enantioselectivities of up to 94:6 er. Initial mechanistic investigations suggest that no free chlorine is formed, and by replacement of the chloride by fluoride, enantioselective chlorofluorinations of alkenes are possible.

Original language	English
Pages (from-to)	9239-9243
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	58
Issue number	27
DOIs	https://doi.org/10.1002/anie.201901777
Publication status	Published - 1 Jul 2019

Keywords

alkenes
dichlorination
enantioselectivity
halogenation
organocatalysis

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10.1002/anie.201901777

Manuscript_Hennecke_PureAccepted author manuscript, 644 KBLicence: Unspecified

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title = "Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes",

abstract = "The use of a new class of unsymmetrical cinchona-alkaloid-based, phthalazine-bridged organocatalysts enabled the highly enantioselective dichlorination of unfunctionalized alkenes. In combination with the electrophilic chlorinating agent 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and triethylsilyl chloride (TES-Cl) as the source of nucleophilic chloride, 1-aryl-2-alkyl alkenes were dichlorinated with enantioselectivities of up to 94:6 er. Initial mechanistic investigations suggest that no free chlorine is formed, and by replacement of the chloride by fluoride, enantioselective chlorofluorinations of alkenes are possible.",

keywords = "alkenes, dichlorination, enantioselectivity, halogenation, organocatalysis",

author = "Volker Wedek and {Van Lommel}, Ruben and Daniliuc, {Constantin G.} and {De Proft}, Frank and Ulrich Hennecke",

year = "2019",

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doi = "10.1002/anie.201901777",

language = "English",

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journal = "Angewandte Chemie International Edition",

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T1 - Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes

AU - Wedek, Volker

AU - Van Lommel, Ruben

AU - Daniliuc, Constantin G.

AU - De Proft, Frank

AU - Hennecke, Ulrich

PY - 2019/7/1

Y1 - 2019/7/1

N2 - The use of a new class of unsymmetrical cinchona-alkaloid-based, phthalazine-bridged organocatalysts enabled the highly enantioselective dichlorination of unfunctionalized alkenes. In combination with the electrophilic chlorinating agent 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and triethylsilyl chloride (TES-Cl) as the source of nucleophilic chloride, 1-aryl-2-alkyl alkenes were dichlorinated with enantioselectivities of up to 94:6 er. Initial mechanistic investigations suggest that no free chlorine is formed, and by replacement of the chloride by fluoride, enantioselective chlorofluorinations of alkenes are possible.

AB - The use of a new class of unsymmetrical cinchona-alkaloid-based, phthalazine-bridged organocatalysts enabled the highly enantioselective dichlorination of unfunctionalized alkenes. In combination with the electrophilic chlorinating agent 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and triethylsilyl chloride (TES-Cl) as the source of nucleophilic chloride, 1-aryl-2-alkyl alkenes were dichlorinated with enantioselectivities of up to 94:6 er. Initial mechanistic investigations suggest that no free chlorine is formed, and by replacement of the chloride by fluoride, enantioselective chlorofluorinations of alkenes are possible.

KW - alkenes

KW - dichlorination

KW - enantioselectivity

KW - halogenation

KW - organocatalysis

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U2 - 10.1002/anie.201901777

DO - 10.1002/anie.201901777

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

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Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes

Abstract

Keywords

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(R,R)-1,2-dichloro-1,2,3,4-tetrahydronaphthalene

1-[(4-bromophenyl)sulfonyl]-3,4-dichloro-1,2,3,4-tetrahydroquinoline

5,6-dichloro-6,7,8,9-tetrahydro-5H-benzo[7]annulene

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Organocatalytic, Enantioselective Dichlorination of Unfunctionalized Alkenes

Abstract

Keywords

Access to Document

Other files and links

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Datasets

(R,R)-1,2-dichloro-1,2,3,4-tetrahydronaphthalene

1-[(4-bromophenyl)sulfonyl]-3,4-dichloro-1,2,3,4-tetrahydroquinoline

5,6-dichloro-6,7,8,9-tetrahydro-5H-benzo[7]annulene

Cite this