Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Bradley B. Gilbert; Stanley T.C. Eey; Pavel Ryabchuk; Olivia Garry; Scott E. Denmark

doi:10.1016/j.tet.2019.05.054

Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Bradley B. Gilbert, Stanley T.C. Eey, Pavel Ryabchuk, Olivia Garry, Scott E. Denmark

Chemistry

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

Abstract

The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.

Original language	English (US)
Pages (from-to)	4086-4098
Number of pages	13
Journal	Tetrahedron
Volume	75
Issue number	31
DOIs	https://doi.org/10.1016/j.tet.2019.05.054
State	Published - Aug 2 2019

Keywords

Electrophilic selenium
Enantioselective dichlorination
Redox catalysis

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Online availability

10.1016/j.tet.2019.05.054

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title = "Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes",

abstract = "The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.",

keywords = "Electrophilic selenium, Enantioselective dichlorination, Redox catalysis",

author = "Gilbert, {Bradley B.} and Eey, {Stanley T.C.} and Pavel Ryabchuk and Olivia Garry and Denmark, {Scott E.}",

note = "Funding Information: The authors acknowledge the National Science Foundation (NSF CHE1664376 ) for financial support. We also thank the UIUC SCS support facilities (microanalysis, mass spectrometry, and NMR spectroscopy) for their assistance. Publisher Copyright: {\textcopyright} 2019 Elsevier Ltd",

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doi = "10.1016/j.tet.2019.05.054",

language = "English (US)",

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AU - Gilbert, Bradley B.

AU - Eey, Stanley T.C.

AU - Ryabchuk, Pavel

AU - Garry, Olivia

AU - Denmark, Scott E.

N1 - Funding Information: The authors acknowledge the National Science Foundation (NSF CHE1664376 ) for financial support. We also thank the UIUC SCS support facilities (microanalysis, mass spectrometry, and NMR spectroscopy) for their assistance. Publisher Copyright: © 2019 Elsevier Ltd

PY - 2019/8/2

Y1 - 2019/8/2

N2 - The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.

AB - The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.

KW - Electrophilic selenium

KW - Enantioselective dichlorination

KW - Redox catalysis

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Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes

Abstract

Keywords

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