Oxone-Mediated Radical C-C Bond Acetmethylation/Arylation of Methylenecyclopropanes and Vinylcyclopropanes with alpha-Alkyl Ketones: Facile Access to Oxoalkyl-Substituted 3,4-Dihydronaphthalenes

• Published in: Journal of organic chemistry Vol. 84; no. 9; pp. 5413 - 5424
• Main Authors: Liu, Yu, Wang, Qiao-Lin, Chen, Zan, Zhou, Quan, Li, Hua, Xu, Wen-Yuan, Xiong, Bi-Quan, Tang, Ke-Wen
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Chemical Soc 03.05.2019
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; FUNCTIONALIZATION; AMINO CARBONYL-COMPOUNDS; C(SP)-H BONDS; EFFICIENT SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; CYCLIC ETHERS; N-OXIDES; GAMMA-LACTONES; METAL-SALTS; H ACTIVATION
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.9b00407

An efficient oxone-mediated radical carbon-carbon sigma-bond acetmethylation/arylation of methylenecyclopropanes with alpha-C(sp(3))-H bonds of ketones is described for the preparation of 2-(2-oxopropyl)-3,4-dihydronaphthalenes. This acetmethylation/arylation undergoes a series of alpha-C(sp(3))-H bond activation, carbon-carbon double bond acetmethylation, carbon-carbon sigma-bond cleavage, and cyclization with intramolecular aromatic ring. The experimental result indicates that the carbon-carbon sigma-bond acetmethylation/ arylation transformation contains a radical process. The difunctionalization method can also be applied to carbon-carbon sigma- bond acetmethylation/arylation of vinylcyclopropanes with ketones. This strategy offers an efficient and convenient method for acetmethylation/arylation of a carbon-carbon sigma-bond with a alpha-carbonyl radical and an aromatic carbon in one pot, building two new carbon-carbon bonds.