Issue 3, 2013
From the journal:

Chemical Science

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

Yuri Iwai,a   Takashi Ozaki,a   Ryo Takita,a   Masanobu Uchiyama,a   Jun Shimokawaa  and  Tohru Fukuyama*a  

* Corresponding authors

a Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
E-mail: fukuyama@mol.f.u-tokyo.ac.jp
Fax: +81-(0)-3-5802-8694
Tel: +81-(0)-3-5841-4777

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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Article information

DOI
https://doi.org/10.1039/C2SC22045H
Article type
Edge Article
Submitted
22 Nov 2012
Accepted
07 Dec 2012
First published
10 Dec 2012

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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