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Chem Sci. 2019 Jan 8;10(9):2678-2686. doi: 10.1039/c8sc05142a. eCollection 2019 Mar 7.

Selective C-C bond formation from rhodium-catalyzed C-H activation reaction of 2-arylpyridines with 3-aryl-2H-azirines.

Author information

1
National Creative Research Initiative Center for Catalytic Organic Reactions , Department of Chemistry , Kangwon National University , Chuncheon 24341 , Republic of Korea . Email: phlee@kangwon.ac.kr.
2
Department of Chemistry , Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 34141 , Republic of Korea . Email: mbaik2805@kaist.ac.kr.
3
Center for Catalytic Hydrocarbon Functionalizations , Institute for Basic Science (IBS) , Daejeon 34141 , Republic of Korea.
4
Department of Bio-Health Technology , Kangwon National University , Chuncheon 24341 , Republic of Korea.

Abstract

A novel method for the synthesis of acylmethyl-substituted 2-arylpyridine derivatives using 3-aryl-2H-azirines was developed by exploring a prototype reaction using DFT-calculations and carrying out targeted experiments guided by the calculated mechanism. 2H-Azirine was initially hypothesized to ring-open at the metal center to furnish familiar metal nitrene complexes that may undergo C-N coupling. Computational studies quickly revealed and prototype experimental work confirmed that neither the formation of the expected metal nitrene complexes nor the C-N coupling were viable. Instead, azirine ring-opening followed by C-C coupling was found to be much more favorable to give imines that readily underwent hydrolysis in aqueous conditions to form acylmethyl-substituted products. This new method was highly versatile and selective toward a wide range of substrates with high functional group tolerance. The utility of the new method is demonstrated by a convenient one-pot synthesis of biologically relevant heterocycles such as pyridoisoindole and pyridoisoqunolinone.

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