- Diastereoselective olefin amidoacylationviaphotoredox PCET/nickel-dual catalysis: reaction scope and mechanistic insights
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The selective 1,2-aminoacylation of olefins provides opportunities for the rapid construction of nitrogen-containing molecules. However, the lack of CO-free acylation reactions has limited their application. By using photoredox proton-coupled electron transfer (PCET)/Ni dual-catalysis, a highly regio- and diastereoselective amidoacylation of unactivated olefins has been developed. Various acyl electrophiles are compatible, including alkyl- and aryl acyl chlorides and anhydrides, as well asin situactivated carboxylic acids. Hammett studies and other mechanistic experiments to elucidate features of the diastereoselectivity, a transient absorption study of the PCET step, as well as computational evidence, provide an in-depth understanding of the disclosed transformation.
- Anna, Jessica M.,Hong, Xin,Molander, Gary A.,Saeednia, Borna,Zhang, Shuo-Qing,Zheng, Shuai,Zhou, Jiawang
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p. 4131 - 4137
(2020/05/13)
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- Base-catalyzed carbon-carbon bond formation reactions of ω-hydroxylactams
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Active methylene compounds such as methyl ketones, 1,3-dicarbonyl systems and nitromethane condense under the influence of base with ω-hydroxylactams, thereby forming α-alkylated nitrogen heterocycles.The ease of alkylation is detemined by the position of a tautomeric equilibrium between ω-hydroxylactam and the open-chain amide-aldehyde, which is dependent upon the type of N-substituent and upon the lactam ring size.Some applications for the products obtained are indicated.
- Speckamp, W. N.,Boer, J. J. J. de
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p. 410 - 414
(2007/10/02)
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