Synlett 2019; 30(16): 1891-1894
DOI: 10.1055/s-0037-1611920
letter
© Georg Thieme Verlag Stuttgart · New York

Ruthenium-Catalyzed, Microwave-Mediated [2+2+2] Cycloaddition: A Useful Combination for the Synthesis of 2-Aminopyridines

C. Tran
,
M. Haddad
,
PSL Research University, Chimie ParisTech, CNRS, Institute of Chemistry for Life and Health Sciences, CSB2D team, 11 Rue Pierre et Marie Curie, Paris, 75005 Paris, France   Email: virginie.vidal@chimie-paristech.fr
› Author Affiliations

We thank the Ministère de l'Enseignement Supérieur de la Recherche et de l’Innovation, Chimie ParisTech (C.T.) and the CNRS for financial support.
Further Information

Publication History

Received: 19 July 2019

Accepted after revision: 20 August 2019

Publication Date:
03 September 2019 (online)

Abstract

A ruthenium-catalyzed [2+2+2] cycloaddition between α,ω-diynes and cyanamides is reported under microwave irradiation to access 2-aminopyridines. In contrast to the classical thermal conditions, this atom-economical sustainable protocol allows access to diverse functionalized 2-aminopyridine derivatives with high yields and excellent regioselectivities in MeTHF with short reaction times.

Supporting Information

 
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      Diynes 1a, 1b, and 1h were prepared according to:
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  • 40 General Procedure for the Ru-Catalyzed [2+2+2] Cycloaddition of Diynes and Cyanamides In a microwave tube equipped with [Cp*Ru(CH3CN)3]PF6 (2 mol%) and diyne 1 (0.2–0.5 mmol, 1.0 equiv), a solution of cyanamide 2 (0.3–0.6 mmol) in MeTHF (1 mL) was added under an argon atmosphere. The reaction mixture was then stirred at 50 °C, with 50 W irradiation for 15 min in a microwave reactor (fixed power mode). The crude mixture was concentrated under reduced pressure. The dark oil was then filtered through a silica pad, washing with MeTHF, or purified by flash chromatography on silica gel. In some cases,the excess cyanamide was removed by bulb-to-bulb distillation.
  • 41 Although the cycloadduct 3c was obtained in moderate yield under thermal conditions, a side product was observed38e in 27% yield. The microwave irradiation minimizes the formation of side or degradation products.