Construction of a quaternary stereogenic center by asymmetric hydroformylation: a straightforward method to prepare chiral alpha-quaternary amino acids

Zhang, Dequan1; Wen, Jialin1,2; Zhang, Xumu1

2022-06-01

10.1039/d2sc02139k

Chemical Science   影响因子和分区

2041-6520

2041-6539

The construction of chiral quaternary carbon stereocenters has been a long-standing challenge in organic chemistry. Particularly, alpha-quaternary amino acids that are of high importance in biochemistry still lack a straightforward synthetic method. We here reported a hydroformylation approach to access chiral quaternary stereogenic centers, which has been a long-standing challenge in transition metal catalysis. alpha,beta-Unsaturated carboxylic acid derivatives undergo hydroformylation with a rhodium catalyst to generate an alpha-quaternary stereocenter under mild conditions. By using this method, a variety of chiral alpha-quaternary amino acids could be synthesized with satisfactory enantioselectivity. In-depth investigation revealed that the regioselectivity is dramatically influenced by the electronic properties of the substituents attached to the target C=C bond. By applying NMR and DFT analyses, the chiral environment of a rhodium/Yanphos complex was depicted, based on which a substrate-catalyst interaction model was proposed.

SCI ; EI

英语

NI论文

第一 ; 通讯

Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000806432000001

ROYAL SOC CHEMISTRY

20222412225339

Amino acids ; Catalysts ; Electronic properties ; Rhodium compounds ; Stereochemistry ; Transition metals

Metallurgy and Metallography:531 ; Chemistry:801 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China

Zhang, Dequan,Wen, Jialin,Zhang, Xumu. Construction of a quaternary stereogenic center by asymmetric hydroformylation: a straightforward method to prepare chiral alpha-quaternary amino acids[J]. Chemical Science,2022,13:7215-7223.

Zhang, Dequan,Wen, Jialin,&Zhang, Xumu.(2022).Construction of a quaternary stereogenic center by asymmetric hydroformylation: a straightforward method to prepare chiral alpha-quaternary amino acids.Chemical Science,13,7215-7223.

Zhang, Dequan,et al."Construction of a quaternary stereogenic center by asymmetric hydroformylation: a straightforward method to prepare chiral alpha-quaternary amino acids".Chemical Science 13(2022):7215-7223.