126497-27-6Relevant articles and documents
Enantioselective Hydrogenation of Tetrasubstituted α,β-Unsaturated Carboxylic Acids Enabled by Cobalt(II) Catalysis: Scope and Mechanistic Insights
Du, Xiaoyong,Xiao, Ye,Yang, Yuhong,Duan, Ya-Nan,Li, Fangfang,Hu, Qi,Chung, Lung Wa,Chen, Gen-Qiang,Zhang, Xumu
supporting information, p. 11384 - 11390 (2021/04/09)
Chiral carboxylic acids are important compounds because of their prevalence in pharmaceuticals, natural products and agrochemicals. Asymmetric hydrogenation of α,β-unsaturated carboxylic acids has been widely recognized as one of the most efficient synthetic approaches to afford such compounds. Although related asymmetric hydrogenation of di- and trisubstituted unsaturated acids with noble metals is well established, asymmetric hydrogenation of challenging tetrasubstituted α,β-unsaturated carboxylic acids is rarely reported. We demonstrate enantioselective hydrogenation of cyclic and acyclic tetrasubstituted α,β-unsaturated carboxylic acids via cobalt(II) catalysis. This protocol showed broad substrate scope and gave chiral carboxylic acids in good yields with excellent enantiocontrol (up to 98 % yield and 99 % ee). Combined experimental and computational mechanistic studies support a CoII catalytic cycle involving migratory insertion and σ-bond metathesis processes. DFT calculations reveal that enantioselectivity may originate from the steric effect between the phenyl groups of the ligand and the substrate.
Ni-Catalyzed Carboxylation of Unactivated Alkyl Chlorides with CO2
B?rjesson, Marino,Moragas, Toni,Martin, Ruben
, p. 7504 - 7507 (2016/07/06)
A catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl chlorides with CO2 at atmospheric pressure is described. This protocol represents the first intermolecular cross-electrophile coupling of unactivated alkyl chlorides, thus leading to new knowledge in the cross-coupling arena.
Oxidative rearrangement of tertiary propargylic alcohols
Rodríguez, Arantxa,Moran, Wesley J.
, p. 102 - 104 (2013/02/23)
An oxidative rearrangement of tertiary alcohols mediated by m-CPBA is described that generates tetrasubstituted alkenes with a carboxylic acid substituent. The mechanism of the reaction is proposed to proceed through epoxidation of the alkyne to form an o
