Pàmies Oscar, Margalef Jèssica, Cañellas Santiago, James Jinju, Judge Eric, Guiry Patrick J, Moberg Christina, Bäckvall Jan-E, Pfaltz Andreas, Pericàs Miquel A, Diéguez Montserrat
Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C/Marcel·lí Domingo, 1, 43007 Tarragona, Spain.
Discovery Sciences, Janssen Research and Development, Janssen-Cilag, S.A. Jarama 75A, 45007, Toledo, Spain.
Chem Rev. 2021 Apr 28;121(8):4373-4505. doi: 10.1021/acs.chemrev.0c00736. Epub 2021 Mar 19.
This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.
本综述汇编了对映选择性钯催化的烯丙基取代、脱羧烯丙基取代和氧化烯丙基取代的发展历程、机理认识及最新进展。对于每个反应，收集了催化数据及其在合成更复杂分子中的应用实例。还包括我们讨论高选择性关键机理方面以及与其他金属比较（优缺点）的章节。对于钯催化的不对称烯丙基取代，催化数据根据所使用亲核试剂的类型进行分组。由于使用稳定碳亲核试剂和杂亲核试剂的突出地位，已开发出许多手性配体。为了更好地比较结果，按配体类型对其进行分组展示。钯催化的不对称脱羧反应主要由PHOX或特罗斯特配体促进，这使得按时间顺序组织本节内容成为合理的做法。对于不对称氧化烯丙基取代，结果根据所使用亲核试剂的类型进行分组。
