Synthesis 2019; 51(16): 3109-3116
DOI: 10.1055/s-0037-1612423
paper
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Diarylacetylenes Bearing Electron-Withdrawing Groups via the Smiles Rearrangement

Robert Bujok
,
Mieczysław Mąkosza*
Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland   Email: robert.bujok@icho.edu.pl   Email: mieczyslaw.makosza@icho.edu.pl
› Author Affiliations
This work was supported by the Narodowe Centrum Nauki (National Science Centre; grant UNO 2014/15/B/ST5/0218).
Further Information

Publication History

Received: 30 January 2019

Accepted after revision: 05 March 2019

Publication Date:
24 April 2019 (online)


Abstract

Nitrobenzyl benzothiazol-2-yl sulfones and nitrobenzyl 1-phenyl-1H-tetrazol-5-yl sulfones react with chlorides of aromatic acids to form β-acyl derivatives. These products undergo the Smiles rearrangement resulting in the formation of the corresponding nitrophenyl arylacetylenes in 50–60% overall yields (approx. 75% per step). Sulfones bearing CF3 or CN groups instead of a NO2 substituent form mixtures of the acetylenes in moderate yields and benzyl aryl ketones in yields above 40%.

Supporting Information