15118-68-0Relevant academic research and scientific papers
Selective photoredox decarboxylation of α-ketoacids to allylic ketones and 1,4-dicarbonyl compounds dependent on cobaloxime catalysis
Zhang, Hong,Xiao, Qian,Qi, Xu-Kuan,Gao, Xue-Wang,Tong, Qing-Xiao,Zhong, Jian-Ji
supporting information, p. 12530 - 12533 (2020/11/02)
A photoredox/cobaloxime co-catalyzed coupling reaction of α-ketoacids and methacrylates to obtain allylic ketones is described. Without the cobaloxime catalyst, 1,4-dicarbonyl compounds are generated. The cobaloxime catalyst enables dehydrogenation to generate the formation of new olefins. The generality, good substrate scope and mild conditions are good features in the photoredox/cobaloxime catalysis protocol, and this method will provide new opportunities for the functionalization of more olefins.
Organic Dye-Catalyzed Intermolecular Radical Coupling of α-Bromocarbonyls with Olefins: Photocatalytic Synthesis of 1,4-Ketocarbonyls Using Air as an Oxidant
Roy Chowdhury, Soumyadeep,Singh, Deepak,Hoque, Injamam Ul,Maity, Soumitra
, p. 13939 - 13950 (2020/11/20)
An organic dye-catalyzed visible light-promoted ketocarbonylation protocol of vinyl arenes has been disclosed with the help of α-bromocarbonyls where aerial oxygen played a role of an oxidant to install the keto-oxygen functionality. This unique process i
Visible light-induced intermolecular radical addition: Facile access to γ-ketoesters from alkyl-bromocarboxylates and enamines
Hu, Bei,Chen, Haixia,Liu, Yan,Dong, Wuheng,Ren, Kai,Xie, Xiaomin,Xu, Hao,Zhang, Zhaoguo
supporting information, p. 13547 - 13550 (2015/01/09)
A highly efficient addition of alkyl α-bromocarboxylates to enamines by visible light-induced photoredox catalysis is reported. Compared with traditional methods, the reaction described here provided an alternative route for the construction of valuable γ-ketoesters in generally good yields.
Co-catalyzed synthesis of 1,4-dicarbonyl compounds using TBHP oxidant
Zhang, Feng,Du, Peng,Chen, Jijun,Wang, Hongxiang,Luo, Qiang,Wan, Xiaobing
supporting information, p. 1932 - 1935 (2014/05/06)
A Co-catalyzed reaction for the construction of 1,4-dicarbonyls has been reported in which cascade organocobalt addition/trapping/Kornblum-DeLaMare rearrangement were involved. In view of the easy availability of starting materials, wide substrate scope, high functionality tolerance, and operational simplicity, this protocol constituted a simple, practical, and powerful alternative compared with previous approaches.
Enantioselective TADMAP-catalyzed carboxyl migration reactions for the synthesis of stereogenic quaternary carbon
Shaw, Scott A.,Aleman, Pedro,Christy, Justin,Kampf, Jeff W.,Va, Porino,Vedejs, Edwin
, p. 925 - 934 (2007/10/03)
The chiral, nucleophilic catalyst TADMAP [1, 3-(2,2,2-triphenyl-1- acetoxyethyl)-4-(dimethylamino)-pyridine] has been prepared from 3-lithio-4-(dimethylamino)pyridine (5) and triphenylacetaldehyde (3), followed by acylation and resolution. TADMAP catalyzes the carboxyl migration of oxazolyl, furanyl, and benzofuranyl enol carbonates with good to excellent levels of enantioselection. The oxazole reactions are especially efficient and are used to prepare chiral lactams (23) and lactones (30) containing a quaternary asymmetric carbon. TADMAP-catalyzed carboxyl migrations in the indole series are relatively slow and proceed with inconsistent enantioselectivity. Modeling studies (B3LYP/6-31G*) have been used in qualitative correlations of catalyst conformation, reactivity, and enantioselectivity.
Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis
Shaw, Scott A.,Aleman, Pedro,Vedejs, Edwin
, p. 13368 - 13369 (2007/10/03)
TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps
Synthesis of 1,4-Keto Esters and 1,4-Diketones via Palladium-Catalyzed Acylation of Siloxycyclopropanes. Synthetic and Mechanistic Studies
Fujimura, Tsutomu,Aoki, Satoshi,Nakamura, Eiichi
, p. 2809 - 2821 (2007/10/02)
The reaction of a variety of siloxycyclopropanes with acid chlorides in the presence of a catalytic amount of a palladium/phosphine complex gives 1,4-dicarbonyl compounds to good yield. 1-Alkoxy-1-(trialkylsiloxy)-cyclopropanes react with both aromatic and aliphatic acid chlorides in chloroform to give 1,4-keto esters.Synthesis of 1,4-diketones by the acylation of 1-alkyl- or 1-aryl-1-siloxycyclopropanes has been achieved by carrying out the reaction if HMPA under 10-20 atm of carbon monoxide.Kinetic studies and product analysis revealed the unique mechanism of this reaction, which involves rate-determining cleavage of the strained cyclopropane carbon-carbon bond with a coordinatively unsaturated acylpalladium chloride complex.Ab initio calculations of hydroxylated cyclopropane model compounds showed that the unique reactivities of the siloxycyclopropanes may be correlated with the molecular orbital properties of these compounds rather than their ground-state structural properties.
