Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

Shermin S. Goh; Sureshbabu Guduguntla; Takashi Kikuchi; Martin Lutz; Edwin Otten; Makoto Fujita; Ben L. Feringa

doi:10.1021/jacs.8b02992

Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

Shermin S. Goh, Sureshbabu Guduguntla, Takashi Kikuchi, Martin Lutz, Edwin Otten, Makoto Fujita, Ben L. Feringa

Institute of Materials Research and Engineering, 2 Fusionopolis Way, Innovis #08-03, Singapore 138634
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima-shi, Tokyo 196-8666, Japan
Department of Applied Chemistry, University of Tokyo, 7-3-1, Hongo, Bukyo-ku, Tokyo 113-8656, Japan

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

Abstract

The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.

Original language	English
Pages (from-to)	7052-7055
Journal	Journal of the American Chemical Society
Volume	140
Issue number	23
DOIs	https://doi.org/10.1021/jacs.8b02992
Publication status	Published - 23 May 2018

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@article{91ef04ffb4bb457aa3e96aff43c886f6,

title = "Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents",

abstract = "The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.",

author = "Goh, {Shermin S.} and Sureshbabu Guduguntla and Takashi Kikuchi and Martin Lutz and Edwin Otten and Makoto Fujita and Feringa, {Ben L.}",

year = "2018",

month = may,

day = "23",

doi = "10.1021/jacs.8b02992",

language = "English",

volume = "140",

pages = "7052--7055",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

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Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents. / Goh, Shermin S.; Guduguntla, Sureshbabu; Kikuchi, Takashi et al.
In: Journal of the American Chemical Society, Vol. 140, No. 23, 23.05.2018, p. 7052-7055.

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

TY - JOUR

T1 - Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

AU - Goh, Shermin S.

AU - Guduguntla, Sureshbabu

AU - Kikuchi, Takashi

AU - Lutz, Martin

AU - Otten, Edwin

AU - Fujita, Makoto

AU - Feringa, Ben L.

PY - 2018/5/23

Y1 - 2018/5/23

N2 - The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.

AB - The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated by the concise stereocontrolled preparation of cyclic amino alcohols, which are privileged chiral structures in natural products and pharmaceuticals and widely used in synthesis and catalysis.

U2 - 10.1021/jacs.8b02992

DO - 10.1021/jacs.8b02992

M3 - Article

SN - 0002-7863

VL - 140

SP - 7052

EP - 7055

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Desymmetrization of meso-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents

Abstract

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