19956-03-7Relevant articles and documents
Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon
Yang, Hui-Yi,Yao, Ya-Hong,Chen, Ming,Ren, Zhi-Hui,Guan, Zheng-Hui
supporting information, p. 7298 - 7305 (2021/05/26)
Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.
Additions of Aldehyde-Derived Radicals and Nucleophilic N-Alkylindoles to Styrenes by Photoredox Catalysis
Klussmann, Martin,Lux, Marcel
supporting information, (2020/04/30)
The consecutive addition of acyl radicals and N-alkylindole nucleophiles to styrenes was established, as well as some additional radical-nucleophile combinations. Both aryl and aliphatic aldehydes give reasonable yields. The reaction proceeds best for α-substituted styrenes, effectively creating a quaternary all-carbon center. Some iridium-based photoredox systems are catalytically active; furthermore, a base is needed in this transformation. Radicals are formed by reductive perester cleavage and hydrogen atom transfer.
Regioselective Diboron-Mediated Semireduction of Terminal Allenes
Gates, Ashley M.,Santos, Webster L.
supporting information, p. 4619 - 4624 (2019/12/11)
A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.