Enantioselective copper-catalyzed allylic substitution reaction with aminohydroxyphosphine ligand

Naohiko Yoshikai; Kotaro Miura; Eiichi Nakamura

doi:10.1002/adsc.200900054

Enantioselective copper-catalyzed allylic substitution reaction with aminohydroxyphosphine ligand

Naohiko Yoshikai, Kotaro Miura, Eiichi Nakamura

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

31 Citations (Scopus)

Abstract

A proline-derived aminohydroxyphosphine ligand induced excellent regio- and enantiose-lectivities (S_N2′: S_N2>94:6, 94-97% ee) in the copper-catalyzed substitution reaction of cinnamyl phosphates with Et₂Zn. A computational modelling study of the reaction pathway suggests that the displacement of the leaving group takes place in an ordered, anti-fashion through simultaneous copper-olefin and zinc-oxygen interactions, which is critical for the enantioselection.

Original language	English
Pages (from-to)	1014-1018
Number of pages	5
Journal	Advanced Synthesis and Catalysis
Volume	351
Issue number	7-8
DOIs	https://doi.org/10.1002/adsc.200900054
Publication status	Published - 2009 May
Externally published	Yes

Keywords

Allylic substitution
C-C bond formation
Copper
Organozinc reagents
Phosphane ligands

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/adsc.200900054

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title = "Enantioselective copper-catalyzed allylic substitution reaction with aminohydroxyphosphine ligand",

abstract = "A proline-derived aminohydroxyphosphine ligand induced excellent regio- and enantiose-lectivities (SN2′: SN2>94:6, 94-97% ee) in the copper-catalyzed substitution reaction of cinnamyl phosphates with Et2Zn. A computational modelling study of the reaction pathway suggests that the displacement of the leaving group takes place in an ordered, anti-fashion through simultaneous copper-olefin and zinc-oxygen interactions, which is critical for the enantioselection.",

keywords = "Allylic substitution, C-C bond formation, Copper, Organozinc reagents, Phosphane ligands",

author = "Naohiko Yoshikai and Kotaro Miura and Eiichi Nakamura",

year = "2009",

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doi = "10.1002/adsc.200900054",

language = "English",

volume = "351",

pages = "1014--1018",

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issn = "1615-4150",

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T1 - Enantioselective copper-catalyzed allylic substitution reaction with aminohydroxyphosphine ligand

AU - Yoshikai, Naohiko

AU - Miura, Kotaro

AU - Nakamura, Eiichi

PY - 2009/5

Y1 - 2009/5

N2 - A proline-derived aminohydroxyphosphine ligand induced excellent regio- and enantiose-lectivities (SN2′: SN2>94:6, 94-97% ee) in the copper-catalyzed substitution reaction of cinnamyl phosphates with Et2Zn. A computational modelling study of the reaction pathway suggests that the displacement of the leaving group takes place in an ordered, anti-fashion through simultaneous copper-olefin and zinc-oxygen interactions, which is critical for the enantioselection.

AB - A proline-derived aminohydroxyphosphine ligand induced excellent regio- and enantiose-lectivities (SN2′: SN2>94:6, 94-97% ee) in the copper-catalyzed substitution reaction of cinnamyl phosphates with Et2Zn. A computational modelling study of the reaction pathway suggests that the displacement of the leaving group takes place in an ordered, anti-fashion through simultaneous copper-olefin and zinc-oxygen interactions, which is critical for the enantioselection.

KW - Allylic substitution

KW - C-C bond formation

KW - Copper

KW - Organozinc reagents

KW - Phosphane ligands

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JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

SN - 1615-4150

IS - 7-8

ER -

Enantioselective copper-catalyzed allylic substitution reaction with aminohydroxyphosphine ligand

Abstract

Keywords

ASJC Scopus subject areas

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