Palladium‐ and Iridium‐Catalyzed Deracemization of Allylic Oxygen Compounds with Oxygen Nucleophiles
Palladium‐ and Iridium‐Catalyzed Deracemization of Allylic Oxygen Compounds with Oxygen Nucleophiles
复制标题
钯和铱催化烯丙基含氧化合物与氧亲核试剂的去消旋化
DOI：
10.1002/ejoc.202201016
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发表时间：
2022
影响因子：
2.8
通讯作者：
H. Gais
中科院分区：
文献类型：
--
作者：
H. Gais
烯丙基氧化合物（AOC）是天然和非天然产物合成中的一类重要的通用结构单元。催化原位去外消旋是一种有吸引力的方法，用于它们的不对称选择性合成。特别有吸引力的是通过过渡金属催化的动态动力学不对称转化（DYKAT）与氧亲核试剂（ONus）的AOC去外消旋化。本文综述了钯催化的外消旋烯丙基羧酸酯、乙烯基环氧乙烷和乙烯基二氧戊环酮与羧酸酯、碳酸氢盐、醇、酚、肟、二酚和水的DYKAT反应以及铱催化的外消旋烯丙醇、酰亚胺和羧酸酯与醇和羧酸的DYKAT反应的相关方面。在讨论中包括的是钯催化的去对称化的meso-环烯烃双（羧酸酯）与碳酸氢盐。虽然Trost的双膦基苯甲酰胺、Zhou的螺环亚磷酰胺和Feringa的BINOL亚磷酰胺是钯催化的DYKAT中的高效配体，但Carreira-Dorta的BINOL亚磷酰胺-烯烃是铱催化的DYKAT中的优异配体。本文还讨论了η3-烯丙基钯-双膦基苯甲酰胺和η3-烯丙基铱-BINOL-亚磷酰胺-烯烃配合物以及相应催化剂的机理和结构方面。
Allylic oxygen compounds (AOCs) are an important class of versatile building blocks in natural and non‐natural product synthesis. Catalytic in‐situ deracemization is an attractive means for their enantioselective synthesis. Particularly attractive is the deracemization of AOCs through transition metal‐catalyzed dynamic kinetic asymmetric transformation (DYKAT) with oxygen nucleophiles (ONus). This review describes pertinent aspects of the palladium‐catalyzed DYKAT of racemic allylic carboxylates, vinyl oxiranes and vinyl dioxolanones with carboxylates, hydrogen carbonate, alcohols, phenols, oximes, diosphenols and water and the iridium‐catalyzed DYKAT of racemic allylic alcohols, imidates and carboxylates with alcohols and carboxylic acids. Included in the discussion is the palladium‐catalyzed desymmetrization ofmeso‐cycloalkene bis(carboxylates) with hydrogen carbonate. While Trost's bisphosphinobenzamides, Zhou's spiro‐phosphoramidite and Feringa's BINOL‐phosphoramidite are highly efficient ligands in palladium‐catalyzed DYKAT, Carreira‐Dorta's BINOL‐phosphoramidite‐olefin is an excellent ligand in iridium‐catalyzed DYKAT. This review also discusses mechanistic and structural aspects of η3‐allylpalladium‐bisphosphinobenzamide and η3‐allyliridium‐BINOL‐phosphoramidite‐olefin complexes and of the corresponding catalysts.