Metal–free One–pot Synthesis of Functionalized Carbazoles. Issue 7 (2nd March 2017)

• Record Type: Journal Article
• Authors: Tao, Sheng; Wang, Rong‐Jie; Liu, Ning; Dai, Bin
• Is Part Of: ChemistrySelect. Volume 2:Issue 7(2017)
• Page Start: 2282
• Page End: 2287
• Publication Date: 2017-03-02
• Subjects: carbazole -- metal-free -- N-arylation -- one-pot -- site-selectivity; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201700128
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: A distinct dichotomy in product distribution was initially observed in metal‐free domino C−N and C−O bond forming reaction of carbazoles with aryl halides or benzyl halides. The fluoride group in halogenated fluorobenzenes almost exclusively undergoes double nucleophilic substitution with hydroxy group and amino group bearing carbazole ring. The reaction was found to occur preferentially at benzyl‐halogen atom when halobenzyl halides were present. Controlling experiments found that first coupling occurred with excellent site‐selectivity in favor of the hydroxy group on carbazole. A wide range of halogenated functionalized carbazoles, which have a wide utility for organic synthesis, polymer chemistry, and advanced functional materials application, were tolerated. Abstract : We discovered a remarkable substrate‐controlled product divergence in metal‐free domino C−N and C−O bond forming reaction of carbazoles with aryl halides or halobenzyl halides. The fluoride group in halogenated fluorobenzenes almost exclusively undergoes double nucleophilic substitution with hydroxy group and amino group bearing carbazole ring; the reaction was found to occur preferentially at the benzyl‐halogen atom when halobenzyl halides were present.