Remote steric effects of C2-symmetric planar-chiral terpyridine ligands on copper-catalyzed asymmetric cyclopropanation reactions

Nanako Mugishima; Nobuhiro Kanomata; Norihiko Akutsu; Hironobu Kubota

doi:10.1016/j.tetlet.2015.02.103

Remote steric effects of C₂-symmetric planar-chiral terpyridine ligands on copper-catalyzed asymmetric cyclopropanation reactions

Nanako Mugishima, Nobuhiro Kanomata, Norihiko Akutsu, Hironobu Kubota

Research output: Contribution to journal › Article

6 Citations (Scopus)

Abstract

A series of enantioselective cyclopropanation reactions of substituted alkenes with diazoacetates was investigated in the presence of Cu(OTf)₂ with C₂-symmetric planar-chiral bridged 2,2′:6′,2″-terpyridines. Planar-chiral terpyridine-copper complexes exhibited moderate diastereomeric excesses with good enantioselectivities of cis-cyclopropane products in catalytic asymmetric cyclopropanation reactions of various styrene derivatives with ethyl diazoacetate. A remote steric effect was found to enhance enantioselectivity for the cyclopropanation induced by a sterically demanding substituent beyond the ansa-bridge of pyridinophane ligands on the other side of the reaction site as a relay of steric influences through flexible cyclophane bridges.

Original language	English
Pages (from-to)	1898-1903
Number of pages	6
Journal	Tetrahedron Letters
Volume	56
Issue number	14
DOIs	https://doi.org/10.1016/j.tetlet.2015.02.103
Publication status	Published - 2015 Apr 1

Keywords

Asymmetric cyclopropanation
Copper carbenoid
Planar chirality
Remote steric effect
Terpyridine

ASJC Scopus subject areas

Biochemistry
Organic Chemistry
Drug Discovery

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Mugishima, N., Kanomata, N., Akutsu, N., & Kubota, H. (2015). Remote steric effects of C₂-symmetric planar-chiral terpyridine ligands on copper-catalyzed asymmetric cyclopropanation reactions. Tetrahedron Letters, 56(14), 1898-1903. https://doi.org/10.1016/j.tetlet.2015.02.103

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abstract = "A series of enantioselective cyclopropanation reactions of substituted alkenes with diazoacetates was investigated in the presence of Cu(OTf)2 with C2-symmetric planar-chiral bridged 2,2′:6′,2″-terpyridines. Planar-chiral terpyridine-copper complexes exhibited moderate diastereomeric excesses with good enantioselectivities of cis-cyclopropane products in catalytic asymmetric cyclopropanation reactions of various styrene derivatives with ethyl diazoacetate. A remote steric effect was found to enhance enantioselectivity for the cyclopropanation induced by a sterically demanding substituent beyond the ansa-bridge of pyridinophane ligands on the other side of the reaction site as a relay of steric influences through flexible cyclophane bridges.",

keywords = "Asymmetric cyclopropanation, Copper carbenoid, Planar chirality, Remote steric effect, Terpyridine",

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AU - Kubota, Hironobu

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N2 - A series of enantioselective cyclopropanation reactions of substituted alkenes with diazoacetates was investigated in the presence of Cu(OTf)2 with C2-symmetric planar-chiral bridged 2,2′:6′,2″-terpyridines. Planar-chiral terpyridine-copper complexes exhibited moderate diastereomeric excesses with good enantioselectivities of cis-cyclopropane products in catalytic asymmetric cyclopropanation reactions of various styrene derivatives with ethyl diazoacetate. A remote steric effect was found to enhance enantioselectivity for the cyclopropanation induced by a sterically demanding substituent beyond the ansa-bridge of pyridinophane ligands on the other side of the reaction site as a relay of steric influences through flexible cyclophane bridges.

AB - A series of enantioselective cyclopropanation reactions of substituted alkenes with diazoacetates was investigated in the presence of Cu(OTf)2 with C2-symmetric planar-chiral bridged 2,2′:6′,2″-terpyridines. Planar-chiral terpyridine-copper complexes exhibited moderate diastereomeric excesses with good enantioselectivities of cis-cyclopropane products in catalytic asymmetric cyclopropanation reactions of various styrene derivatives with ethyl diazoacetate. A remote steric effect was found to enhance enantioselectivity for the cyclopropanation induced by a sterically demanding substituent beyond the ansa-bridge of pyridinophane ligands on the other side of the reaction site as a relay of steric influences through flexible cyclophane bridges.

KW - Asymmetric cyclopropanation

KW - Copper carbenoid

KW - Planar chirality

KW - Remote steric effect

KW - Terpyridine

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