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Microwave‐Promoted Metal‐Free α‐Alkylation of Ketones with Cycloalkanes through Cross‐Coupling of C(sp 3 )−H Bonds
Author(s) -
Wang QianQian,
Wang ZhangXin,
Zhang XinYing,
Fan XueSen
Publication year - 2017
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201700256
Subject(s) - chemistry , alkylation , ketone , metal , radical , atom economy , organic chemistry , coupling reaction , combinatorial chemistry , medicinal chemistry , catalysis
The microwave‐promoted α‐alkylation of ketones with cycloalkanes as alkylating agents under metal‐free conditions is presented. The reaction mechanism involves the DTBP‐initiated (DTBP=di‐ tert ‐butyl peroxide) microwave‐assisted formation of the required cycloalkyl and α‐ketone carbon radicals followed by a selective cross‐coupling step. This is the first example in which simple ketones and 1,3‐diketones have been efficiently alkylated with cycloalkanes under metal‐free conditions through the cross‐dehydrogenative coupling of C(sp 3 )−H bonds. Compared with previous methods, this alkylation protocol has advantages such as the use inexpensive and abundant substrates under metal‐free conditions and its good atom‐economy and sustainability. Moreover, the substituted ketones can be used as intermediates in the preparation of the synthetically and biologically valuable trisubstituted alkenes.