Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Published: July 2017
AI Article Synopsis
Article Abstract
We describe the nickel-catalyzed hydrocarboxylation of ynamides with CO and HO to afford a variety of α-amino-α,β-unsaturated esters with high regioselectivities. The selective α-carboxylation of ynamides with this catalytic protocol is unexpected in view of the electronic bias of ynamides and is in sharp contrast to our previous study in which a stoichiometric amount of Ni(0) was used to form a β-carboxylated product exclusively. We revealed that this unexpected C-C bond formation was induced by the combination of Zn and MgBr.
College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Collaborative Innovation Center of Functionalized Probes for, Chemical Imaging in Universities of Shandong, Institutes of Biomedical Sciences, Shandong Normal University, Jinan, 250014, P. R. China.
We report a stereoselective conversion of terminal alkynes to α-chiral carboxylic acids using a nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction. A simple nickel/BenzP* catalyst displayed high activity in both steps of regioselective hydrocarboxylation of alkynes and subsequent asymmetric transfer hydrogenation. The reaction was successfully applied in enantioselective preparation of three nonsteroidal anti-inflammatory profens (>90 % ees) and the chiral fragment of AZD2716.
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei 230601, P. R. China.
The nickel-catalyzed hydrocarboxylation of alkenes using carbon dioxide has recently become an appealing method to prepare functionalized carboxylic acids with high efficiency and regioselectivity. Herein, density functional theory (DFT) calculations were conducted on the Ni-catalyzed hydrocarboxylation of aryl-/alkyl-substituted alkenes with CO. The α- and β-carboxylation of aromatic and aliphatic olefins originate from distinct catalytic cycles: H-transfer-carboxylation and carboxylation-H-transfer pathways.
We describe the nickel-catalyzed hydrocarboxylation of ynamides with CO and HO to afford a variety of α-amino-α,β-unsaturated esters with high regioselectivities. The selective α-carboxylation of ynamides with this catalytic protocol is unexpected in view of the electronic bias of ynamides and is in sharp contrast to our previous study in which a stoichiometric amount of Ni(0) was used to form a β-carboxylated product exclusively. We revealed that this unexpected C-C bond formation was induced by the combination of Zn and MgBr.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Lu, Shanghai 200032, China.
A nickel-catalyzed three-component hydrocarboxylation of diynes with ZnEt2 and CO2 (1 atm) is disclosed. With this method, symmetric/nonsymmetric diynes could be reacted smoothly with very high stereo- and regioselectivity, affording conjugated 2,4-alkadienoic acids incorporated with five- or six-membered rings efficiently. A stepwise non-oxidative cyclometalation mechanism was proposed based on careful mechanistic studies.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P.R. China.
