70454-09-0Relevant articles and documents
Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch-Selective Pd/Cu Catalyzed Allylic Substitution
Li, Guanlin,Zhao, Ling,Luo, Yicong,Peng, Youbin,Xu, Kai,Huo, Xiaohong,Zhang, Wanbin
supporting information, (2022/04/03)
Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity.
Synthesis and Nuclear Magnetic Resonance Study of 2-Thiazolines
Eggleton, Gordon L.,Bushman, Daniel R.,Whitlock, David W.,Pugh, Darrell K.,Chance, Katherine L.
, p. 351 - 354 (2007/10/02)
A series of 5,5-dimethyl-2-thiazoline-4-carboxylates with a phenyl or methyl group at the 2-position of the ring were prepared from the corresponding methyl or ethyl ester of penicillamine and either methyl benzimidate or ethyl acetimidate.The free acid was obtained by the reaction of penicillamine with benzonitrile to produce 5,5-dimethyl-2-phenyl-2-thiazoline-4-carboxylic acid.Corresponding thiazolines were prepared from cysteine in the same manner.The nuclear magnetic resonance spectra of both series exhibit coupling of the methyl group at the 2-position with the hydrogen at the 4-position.The groups at the 5-position are nonequivalent and in the case of the cysteine series give rise to an ABX system.Further analysis confirms a concentration dependence for this splitting pattern.