Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides

Takuji Hatakeyama; Shingo Ito; Hiroaki Yamane; Masaharu Nakamura; Eiichi Nakamura

doi:10.1016/j.tet.2007.05.087

Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides

Takuji Hatakeyama, Shingo Ito, Hiroaki Yamane, Masaharu Nakamura^*, Eiichi Nakamura

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

A magnesium enamide derived from N-2-(N′,N′-dimethylamino)ethyl imine reacts with primary and secondary alkyl chlorides and fluorides to give an α-alkylated ketone in good to excellent yields upon hydrolysis of the imine moiety. Reactions of the highly nucleophilic magnesium enamide derived from an unsymmetrical ketone take place regioselectively. In addition, the C-C bond formation is stereospecific: a substantial inversion of stereochemistry at the electrophilic carbon center (Walden inversion) was observed, proving its potential utility for the production of optically active compounds.

Original language	English
Pages (from-to)	8440-8448
Number of pages	9
Journal	Tetrahedron
Volume	63
Issue number	35
DOIs	https://doi.org/10.1016/j.tet.2007.05.087
Publication status	Published - Aug 27 2007
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2007.05.087

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title = "Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides",

abstract = "A magnesium enamide derived from N-2-(N′,N′-dimethylamino)ethyl imine reacts with primary and secondary alkyl chlorides and fluorides to give an α-alkylated ketone in good to excellent yields upon hydrolysis of the imine moiety. Reactions of the highly nucleophilic magnesium enamide derived from an unsymmetrical ketone take place regioselectively. In addition, the C-C bond formation is stereospecific: a substantial inversion of stereochemistry at the electrophilic carbon center (Walden inversion) was observed, proving its potential utility for the production of optically active compounds.",

author = "Takuji Hatakeyama and Shingo Ito and Hiroaki Yamane and Masaharu Nakamura and Eiichi Nakamura",

year = "2007",

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T1 - Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides

AU - Hatakeyama, Takuji

AU - Ito, Shingo

AU - Yamane, Hiroaki

AU - Nakamura, Masaharu

AU - Nakamura, Eiichi

PY - 2007/8/27

Y1 - 2007/8/27

N2 - A magnesium enamide derived from N-2-(N′,N′-dimethylamino)ethyl imine reacts with primary and secondary alkyl chlorides and fluorides to give an α-alkylated ketone in good to excellent yields upon hydrolysis of the imine moiety. Reactions of the highly nucleophilic magnesium enamide derived from an unsymmetrical ketone take place regioselectively. In addition, the C-C bond formation is stereospecific: a substantial inversion of stereochemistry at the electrophilic carbon center (Walden inversion) was observed, proving its potential utility for the production of optically active compounds.

AB - A magnesium enamide derived from N-2-(N′,N′-dimethylamino)ethyl imine reacts with primary and secondary alkyl chlorides and fluorides to give an α-alkylated ketone in good to excellent yields upon hydrolysis of the imine moiety. Reactions of the highly nucleophilic magnesium enamide derived from an unsymmetrical ketone take place regioselectively. In addition, the C-C bond formation is stereospecific: a substantial inversion of stereochemistry at the electrophilic carbon center (Walden inversion) was observed, proving its potential utility for the production of optically active compounds.

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U2 - 10.1016/j.tet.2007.05.087

DO - 10.1016/j.tet.2007.05.087

M3 - Article

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SN - 0040-4020

VL - 63

SP - 8440

EP - 8448

JO - Tetrahedron

JF - Tetrahedron

IS - 35

ER -

Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides

Abstract

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