A new combination of " anti-Baldwin" 3- exo-dig cyclization with 1,2-alkynyl migration of 1,4-enynes with simple cycloalkanes was established, enabling C-C breaking and reconstruction to access a wide range of α-alkynyl ketones with generally good yields by FeCl/di- tert-butyl peroxide (DTBP) as a catalytic oxidation system. Radical-induced C(sp)-H functionalization of cycloalkanes was realized, leading to the direct formation of C(sp)-C(sp) and C(sp)-C(sp) bonds. The mechanism for forming α-alkynyl ketones was proposed.
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A general synthesis of azetidines by copper-catalysed photoinduced anti-Baldwin radical cyclization of ynamides.
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Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, 1050, Brussels, Belgium.
A general anti-Baldwin radical 4-exo-dig cyclization from nitrogen-substituted alkynes is reported. Upon reaction with a heteroleptic copper complex in the presence of an amine and under visible light irradiation, a range of ynamides were shown to smoothly cyclize to the corresponding azetidines, useful building blocks in natural product synthesis and medicinal chemistry, with full control of the regioselectivity of the cyclization resulting from a unique and underrated radical 4-exo-dig pathway.
View Article and Find Full Text PDFMerging " Anti-Baldwin" 3- Exo-Dig Cyclization with 1,2-Alkynyl Migration for Radical Alkylalkynylation of Unactivated Olefins.
Org Lett
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School of Chemistry & Materials Science, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials , Jiangsu Normal University, Xuzhou , 221116 , P. R. China.
A new combination of " anti-Baldwin" 3- exo-dig cyclization with 1,2-alkynyl migration of 1,4-enynes with simple cycloalkanes was established, enabling C-C breaking and reconstruction to access a wide range of α-alkynyl ketones with generally good yields by FeCl/di- tert-butyl peroxide (DTBP) as a catalytic oxidation system. Radical-induced C(sp)-H functionalization of cycloalkanes was realized, leading to the direct formation of C(sp)-C(sp) and C(sp)-C(sp) bonds. The mechanism for forming α-alkynyl ketones was proposed.
View Article and Find Full Text PDFAn "anti-Baldwin" 3-exo-dig cyclization: preparation of vinylidene cyclopropanes from electron-poor alkenes.
J Am Chem Soc
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Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Stabilized carbanions undergo an uncommon 3-exodig cyclization onto propargyl halides through an SN2' substitution. Propargyl iodides as electrophiles are necessary to achieve good yields (36-95%) for most substrates, although the usefulness of chlorides and bromides is documented. A variety of monocyclic and bicyclic vinylidene cyclopropanes can be prepared.
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