119458-35-4Relevant academic research and scientific papers
Br?nsted Acid Catalyzed Friedel–Crafts-Type Coupling and Dedinitrogenation Reactions of Vinyldiazo Compounds
Arman, Hadi,Dong, Kuiyong,Doyle, Michael P.,Wherritt, Daniel,Zheng, Haifeng
supporting information, p. 13613 - 13617 (2020/06/10)
The direct Friedel–Crafts-type coupling and dedinitrogenation reactions of vinyldiazo compounds with aromatic compounds using a metal-free strategy are described. This Br?nsted acid catalyzed method is efficient for the formation of α-diazo β-carbocations (vinyldiazonium ions), vinyl carbocations, and allylic or homoallylic carbocation species via vinyldiazo compounds. By choosing suitable nucleophilic reagents to selectively capture these intermediates, both trisubstituted α,β-unsaturated esters, β-indole-substituted diazo esters, and dienes are obtained with good to high yields and selectivity. Experimental insights implicate a reaction mechanism involving the selective protonation of vinyldiazo compounds and the subsequent release of dinitrogen to form vinyl cations that undergo intramolecular 1,3- and 1,4- hydride transfer processes as well as fragmentation.
Pd-catalyzed C-H olefination of (hetero)arenes by using saturated ketones as an olefin source
Shang, Yaping,Jie, Xiaoming,Zhou, Jun,Hu, Peng,Huang, Shijun,Su, Weiping
supporting information, p. 1299 - 1303 (2013/03/13)
Tolerant: By using Pd(OAc)2/PCy3 as a catalyst, both electron-rich aromatic heterocycles and electron-deficient fluorobenzenes undergo the dehydrogenative cross-coupling with (hetero)aryl ethyl ketones in good yields. A broad range of functional groups is tolerated, thus providing a general method for the facile syntheses of chalcones or heterocyclic chalcone analogues. Furthermore, dialkyl ketones can also participate in this transformation. Copyright
Evidence that the availability of an allylic hydrogen governs the regioselectivity of the Wacker oxidation
Gaunt,Yu,Spencer
, p. 1844 - 1845 (2007/10/03)
The allylic hydrogen is found to have a dramatic effect on the regioselectivity of the Wacker oxidation, leading to the postulation that an agostic hydrogen or enyl (σ + π) complex helps to stabilise the key intermediate.
