Synthesis 2019; 51(11): 2318-2322
DOI: 10.1055/s-0037-1610865
paper
© Georg Thieme Verlag Stuttgart · New York

A New Method for the Preparation of Bis(alkylamino)maleonitriles from Aliphatic Isocyanides with TMSCN and Bi(OTf)3

Sayaka Tafuku
,
Takuya Fukuda
,
Kazuhiro Chiba
,
Yoshikazu Kitano*
Laboratory of Bio-organic Chemistry, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu-shi, Tokyo 183-8509, Japan   Email: kitayo@cc.tuat.ac.jp
› Author Affiliations
This work was partially supported by JSPS KAKENHI Grant Number JP16K07867.
Further Information

Publication History

Received: 17 January 2019

Accepted after revision: 04 February 2019

Publication Date:
11 March 2019 (eFirst)

Abstract

Bis(alkylamino)maleonitriles are starting materials for the synthesis of a number of important intermediates, including porphyrazines that serve as dyes, pigments, and models of biologically active substances; hence, the development of improved methods for their preparation is important. Herein, we report a facile new method for the preparation of bis(alkylamino)maleonitriles from isocyanides. Treatment of tert-alkyl isocyanides with trimethylsilyl cyanide (TMSCN) and trimethylsilyl triflate (TMSOTf) in the presence of bismuth(III) triflate [Bi(OTf)3] afforded the corresponding bis(alkylamino)maleonitriles in moderate yields. tert-Alkyl isocyanides bearing a variety of functional groups, including halide, ether, ester, imide, amide, and carbamate, are tolerated under the developed reaction conditions. To the best of our knowledge, this is the first report of a synthetic method for the preparation of bis(alkylamino)maleonitriles in a single step from tertiary alkyl isocyanides.

Supporting Information

 
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