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Issue 3, 2013
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Modified McFadyen–Stevens reaction for a versatile synthesis of aliphatic/aromatic aldehydes: design, optimization, and mechanistic investigations

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Abstract

The traditional McFadyen–Stevens reaction requires harsh alkaline reaction conditions, thus precluding application to the synthesis of aliphatic aldehydes. Our modified McFadyen–Stevens reaction enables the transformation from the N,N-acylsulfonyl hydrazine to the corresponding aldehyde upon treatment with an imidazole–TMS imidazole combination without relying on oxidative or reductive reagents. The reduced basicity and in situ protection of the resulting aldehyde widens the substrate scope to include aliphatic aldehydes, even ones bearing an α-hydrogen atom. Close examination of the side reactions for particular substrates in combination with theoretical considerations via DFT calculations led to a mechanistic understanding of the McFadyen–Stevens reaction involving an acyl diazene and a hydroxy carbene as reasonable intermediates.

Graphical abstract: Modified McFadyen–Stevens reaction for a versatile synthesis of aliphatic/aromatic aldehydes: design, optimization, and mechanistic investigations

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Publication details

The article was received on 22 Nov 2012, accepted on 07 Dec 2012 and first published on 10 Dec 2012


Article type: Edge Article
DOI: 10.1039/C2SC22045H
Citation: Chem. Sci., 2013,4, 1111-1119
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    Modified McFadyen–Stevens reaction for a versatile synthesis of aliphatic/aromatic aldehydes: design, optimization, and mechanistic investigations

    Y. Iwai, T. Ozaki, R. Takita, M. Uchiyama, J. Shimokawa and T. Fukuyama, Chem. Sci., 2013, 4, 1111
    DOI: 10.1039/C2SC22045H

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