Catalytic Asymmetric Intramolecular Cyclopropanation of α-Diazo-α-Silyl Acetate

Saori Inoue; Kotaro Nagatani; Haruka Tezuka; Yunosuke Hoshino; Masahisa Nakada

doi:10.1055/s-0036-1588414

Catalytic Asymmetric Intramolecular Cyclopropanation of α-Diazo-α-Silyl Acetate

Saori Inoue, Kotaro Nagatani, Haruka Tezuka, Yunosuke Hoshino, Masahisa Nakada^*

^*Corresponding author for this work

School of Advanced Science and Engineering

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

14 Citations (Scopus)

Abstract

The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of α-diazo-α-silyl acetates to form oxabicyclo[3.2.1]hexane, which proceeds with high yields and enantioselectivities, is described. The maximum enantiomeric excess observed was 96% ee and the absolute configuration of the products was elucidated. The counteranion of the Cu(I) catalyst was found to play a crucial role in determining the yields and enantioselectivities, with highly anionic counteranions improving both yields and enantioselectivities. Our previously reported model explains the enantiofacial selectivity of the reacting alkene.

Original language	English
Article number	st-2016-u0854-l
Pages (from-to)	1065-1070
Number of pages	6
Journal	Synlett
Volume	28
Issue number	9
DOIs	https://doi.org/10.1055/s-0036-1588414
Publication status	Published - 2017 Jun 1

Keywords

asymmetric catalysis
cyclopropanation
diazo compounds
enantioselectivity
lactones

ASJC Scopus subject areas

Organic Chemistry

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title = "Catalytic Asymmetric Intramolecular Cyclopropanation of α-Diazo-α-Silyl Acetate",

abstract = "The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of α-diazo-α-silyl acetates to form oxabicyclo[3.2.1]hexane, which proceeds with high yields and enantioselectivities, is described. The maximum enantiomeric excess observed was 96% ee and the absolute configuration of the products was elucidated. The counteranion of the Cu(I) catalyst was found to play a crucial role in determining the yields and enantioselectivities, with highly anionic counteranions improving both yields and enantioselectivities. Our previously reported model explains the enantiofacial selectivity of the reacting alkene.",

keywords = "asymmetric catalysis, cyclopropanation, diazo compounds, enantioselectivity, lactones",

author = "Saori Inoue and Kotaro Nagatani and Haruka Tezuka and Yunosuke Hoshino and Masahisa Nakada",

note = "Funding Information: We acknowledge support from the Materials Characterization Central Laboratory, Waseda University, for characterization of new compounds. This work was financially supported in part by a Grant-in-Aid for Scientific Research on Innovative Areas 2707 Middle molecular strategy from MEXT, and by a Waseda University Grant for Special Research Projects. Publisher Copyright: {\textcopyright} Georg Thieme Verlag Stuttgart.New York.",

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AU - Inoue, Saori

AU - Nagatani, Kotaro

AU - Tezuka, Haruka

AU - Hoshino, Yunosuke

AU - Nakada, Masahisa

N1 - Funding Information: We acknowledge support from the Materials Characterization Central Laboratory, Waseda University, for characterization of new compounds. This work was financially supported in part by a Grant-in-Aid for Scientific Research on Innovative Areas 2707 Middle molecular strategy from MEXT, and by a Waseda University Grant for Special Research Projects. Publisher Copyright: © Georg Thieme Verlag Stuttgart.New York.

PY - 2017/6/1

Y1 - 2017/6/1

N2 - The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of α-diazo-α-silyl acetates to form oxabicyclo[3.2.1]hexane, which proceeds with high yields and enantioselectivities, is described. The maximum enantiomeric excess observed was 96% ee and the absolute configuration of the products was elucidated. The counteranion of the Cu(I) catalyst was found to play a crucial role in determining the yields and enantioselectivities, with highly anionic counteranions improving both yields and enantioselectivities. Our previously reported model explains the enantiofacial selectivity of the reacting alkene.

AB - The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of α-diazo-α-silyl acetates to form oxabicyclo[3.2.1]hexane, which proceeds with high yields and enantioselectivities, is described. The maximum enantiomeric excess observed was 96% ee and the absolute configuration of the products was elucidated. The counteranion of the Cu(I) catalyst was found to play a crucial role in determining the yields and enantioselectivities, with highly anionic counteranions improving both yields and enantioselectivities. Our previously reported model explains the enantiofacial selectivity of the reacting alkene.

KW - asymmetric catalysis

KW - cyclopropanation

KW - diazo compounds

KW - enantioselectivity

KW - lactones

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Catalytic Asymmetric Intramolecular Cyclopropanation of α-Diazo-α-Silyl Acetate

Abstract

Keywords

ASJC Scopus subject areas

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