Synfacts 2011(9): 0938-0938  
DOI: 10.1055/s-0030-1260998
Synthesis of Heterocycles
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of NH-Free 3-Substituted Indazoles

Contributor(s): Victor Snieckus, Cédric Schneider
P. Li, J. Zhao, C. Wu, R. C. Larock, F. Shi*
Henan University, Kaifeng, P. R. of China and Iowa State University, Ames, USA
Further Information

Publication History

Publication Date:
19 August 2011 (online)


Reported is the synthesis of 3-substituted indazoles 3 from N-tosylhydrazones 2 and o-(trimethylsilyl)aryl triflates 1 through a [3+2] ­dipolar cycloaddition. This reaction requires the presence of a fluoride source which allows the in situ generation of arynes and diazo compounds from the N-tosylhydrazones 2. It has been demonstrated that CsF was the best fluoride source. The addition of phase-transfer catalyst (TEBAC = [Et3NBn]+Cl-) is required to dissolve the conjugate base of 2. The scope of this reaction has been investigated with different arenes and N-tosylhydrazones [from (hetero)aromatic aldehydes bearing EWG, EDG and sterically hindered]. The unsymmetrical monomethoxybenzyne gave a 4.8:1 mixture of regioisomers, which suggests a [3+2] dipolar cycloaddition through a diazo intermediate. Moreover, N-tosylhydrazones derived from aliphatic aldehydes are not suitable substrates.