The Nef reaction of isocyanides

Fabio La Spisa; Gian Cesare Tron; Laurent El Kaïm

doi:10.1055/s-0033-1338596

The Nef reaction of isocyanides

Fabio La Spisa, Gian Cesare Tron, Laurent El Kaïm

Department of Pharmaceutical Sciences

Research output: Contribution to journal › Review article › peer-review

Abstract

The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intraÂ- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues. 1 Isocyanide Chemistry 2 Isocyanide Interaction with Acyl Chlorides and Analogues 2.1 General Considerations 2.2 Methods of Preparation of α-Keto Imidoyl Chlorides 2.3 Nef Reaction Mechanism 3 Reactivity of α-Keto Imidoyl Chlorides 3.1 General Behavior of α-Keto Imidoyl Chlorides 3.2 Intramolecular Trappings 3.3 Intermolecular Trappings and Three-Component Reactions 4 Extensions of the Nef Reaction 5 Conclusion

Original language	English
Article number	4068
Pages (from-to)	829-841
Number of pages	13
Journal	Synthesis
Volume	46
Issue number	7
DOIs	https://doi.org/10.1055/s-0033-1338596
Publication status	Published - Apr 2014

Keywords

Nef reaction
acyl chlorides
imidoyl chlorides
isocyanides
ketenes

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10.1055/s-0033-1338596

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title = "The Nef reaction of isocyanides",

abstract = "The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intra{\^A}- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues. 1 Isocyanide Chemistry 2 Isocyanide Interaction with Acyl Chlorides and Analogues 2.1 General Considerations 2.2 Methods of Preparation of α-Keto Imidoyl Chlorides 2.3 Nef Reaction Mechanism 3 Reactivity of α-Keto Imidoyl Chlorides 3.1 General Behavior of α-Keto Imidoyl Chlorides 3.2 Intramolecular Trappings 3.3 Intermolecular Trappings and Three-Component Reactions 4 Extensions of the Nef Reaction 5 Conclusion",

keywords = "Nef reaction, acyl chlorides, imidoyl chlorides, isocyanides, ketenes",

author = "{La Spisa}, Fabio and Tron, {Gian Cesare} and {El Ka{\"i}m}, Laurent",

year = "2014",

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doi = "10.1055/s-0033-1338596",

language = "English",

volume = "46",

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journal = "Synthesis",

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TY - JOUR

T1 - The Nef reaction of isocyanides

AU - La Spisa, Fabio

AU - Tron, Gian Cesare

AU - El Kaïm, Laurent

PY - 2014/4

Y1 - 2014/4

N2 - The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intraÂ- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues. 1 Isocyanide Chemistry 2 Isocyanide Interaction with Acyl Chlorides and Analogues 2.1 General Considerations 2.2 Methods of Preparation of α-Keto Imidoyl Chlorides 2.3 Nef Reaction Mechanism 3 Reactivity of α-Keto Imidoyl Chlorides 3.1 General Behavior of α-Keto Imidoyl Chlorides 3.2 Intramolecular Trappings 3.3 Intermolecular Trappings and Three-Component Reactions 4 Extensions of the Nef Reaction 5 Conclusion

AB - The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intraÂ- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues. 1 Isocyanide Chemistry 2 Isocyanide Interaction with Acyl Chlorides and Analogues 2.1 General Considerations 2.2 Methods of Preparation of α-Keto Imidoyl Chlorides 2.3 Nef Reaction Mechanism 3 Reactivity of α-Keto Imidoyl Chlorides 3.1 General Behavior of α-Keto Imidoyl Chlorides 3.2 Intramolecular Trappings 3.3 Intermolecular Trappings and Three-Component Reactions 4 Extensions of the Nef Reaction 5 Conclusion

KW - Nef reaction

KW - acyl chlorides

KW - imidoyl chlorides

KW - isocyanides

KW - ketenes

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U2 - 10.1055/s-0033-1338596

DO - 10.1055/s-0033-1338596

M3 - Review article

SN - 0039-7881

VL - 46

SP - 829

EP - 841

JO - Synthesis

JF - Synthesis

IS - 7

M1 - 4068

ER -

The Nef reaction of isocyanides

Abstract

Keywords

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