铑催化的甲硅烷基乙醛酸酯的不对称芳基化诱导乙醇酸酯醛醇加成反应
Rhodium-Catalyzed Asymmetric Arylation-Induced Glycolate Aldol Additions of Silyl Glyoxylates.
作者信息
Turman Nolan C, Smith Kendrick L, Crawford Evan T, Robins Jacob G, Weber Kathryn M, Liu Shubin, Johnson Jeffrey S
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, 27599-3290, USA.
出版信息
Angew Chem Int Ed Engl. 2023 Oct 16;62(42):e202311554. doi: 10.1002/anie.202311554. Epub 2023 Sep 12.
(Diene)Rh(I) complexes catalyze the stereoselective three-component coupling of silyl glyoxylates, arylboronic acids, and aldehydes to give glycolate aldol products. The participation of Rh-alkoxides in the requisite Brook rearrangement was established through two component Rh-catalyzed couplings of silyl glyoxylates with ArB(OH) to give silyl-protected mandelate derivatives. The intermediacy of a chiral Rh-enolate was inferred through enantioselective protonation using a chiral Rh-catalyst. Diastereoselective three-component couplings with aldehydes as terminating electrophiles to give racemic products were best achieved with a bulky aryl ester on the silyl glyoxylate reagent. Optimal enantioselective couplings were carried out with the tert-butyl ester variant using an anisole-derived enantiopure tricyclo[3.2.2.0 ]nonadiene ligand.
（二烯基）铑（I）配合物催化甲硅烷基乙醛酸酯、芳基硼酸和醛的立体选择性三组分偶联反应，生成乙醇酸酯缩醛产物。通过甲硅烷基乙醛酸酯与ArB(OH)的两组分铑催化偶联反应生成甲硅烷基保护的扁桃酸衍生物，确定了铑醇盐参与必要的布鲁克重排反应。通过使用手性铑催化剂进行对映选择性质子化反应，推断出手性铑烯醇盐中间体的存在。以甲硅烷基乙醛酸酯试剂上的大体积芳基酯进行醛作为终止亲电试剂的非对映选择性三组分偶联反应，以得到外消旋产物，效果最佳。使用茴香醚衍生的对映体纯三环[3.2.2.0]壬二烯配体，对叔丁酯变体进行最佳对映选择性偶联反应。
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