791-31-1Relevant articles and documents
Reactions of carboxamides with vinylsilanes under oxidative conditions
Astakhova, Vera V.,Moskalik, Mikhail Yu.,Shainyan, Bagrat A.
, (2022/01/11)
The reactions of acetamide, benzamide and trifluoroacetamide with trimethyl(vinyl)-, triphenyl(vinyl)-, dimethyl(divinyl)- and diphenyl(divinyl)silanes in the presence of oxidants (t-BuOCl + NaI) or N-bromosuccinimide (NBS) in acetonitrile have been studied. Generally, all unsaturated silanes react with trifluoroacetamide to give the products of haloamidation, whereas with acetamide or benzamide the reaction affords mainly the products of halogenation. The formation of bromoamination product containing the MeCONH moiety in the NBS-induced reaction of trimethylvinylsilane with all studied amides clearly indicates that the reaction proceeds with the solvent (MeCN) interception rather than by the attack of the amide nucleophile. The product of bromoamidation from the NBS-promoted reaction undergoes a base-induced cyclization to the corresponding 1,3-oxazoline in quantitative yield.
Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
supporting information, p. 8988 - 8994 (2021/11/23)
A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
HCl-Catalyzed Aerobic Oxidation of Alkylarenes to Carbonyls
Ding, Ling,Liu, Yuxiu,Niu, Kaikai,Shi, Xiaodi,Song, Hongjian,Wang, Qingmin
, (2021/12/13)
The construction of C?O bonds through C?H bond functionalization remains fundamentally challenging. Here, a practical chlorine radical-mediated aerobic oxidation of alkylarenes to carbonyls was developed. This protocol employed commercially available HCl as a hydrogen atom transfer (HAT) reagent and air as a sustainable oxidant. In addition, this process exhibited excellent functional group tolerance and a broad substrate scope without the requirement for external metal and oxidants. The mechanistic hypothesis was supported by radical trapping, 18O labeling, and control experiments.