College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610068, China.
College of Science Sichuan, Agricultural University, Ya'an, Sichuan, 625014, P.R. China.
Chem Asian J. 2023 Feb 14;18(4):e202201113. doi: 10.1002/asia.202201113. Epub 2023 Jan 16.
The synthetic methodologies for the α-functionalization of free carboxylic acids through the enediolate intermediates are summarized in this review. In general, the enediolates could be generated in situ or transiently from free carboxylic acids with a stoichiometric or catalytic amount of protection reagents, including metal, boron, and silicon reagents. The in situ or transient generated enediolates were subsequently subjected to racemic or asymmetric reactions with various electrophiles, producing the α-functionalized free carboxylic acids in a single step. In addition, the enediolate could undergo an α-oxidation reaction with TEMPO through the radical process.
本文综述了通过烯二酮中间体对游离羧酸进行 α-官能化的合成方法。一般来说，烯二酮可以通过化学计量或催化量的保护试剂（包括金属、硼和硅试剂）原位或瞬时从游离羧酸中生成。原位或瞬时生成的烯二酮随后与各种亲电试剂进行外消旋或不对称反应，一步即可得到α-官能化的游离羧酸。此外，烯二酮还可以通过自由基过程与 TEMPO 发生α-氧化反应。
