Ren, Xinyi; Wang, Zhen; Shen, Chaoren; Tian, Xinxin; Tang, Lin; Ji, Xiaolei; Dong, Kaiwu published their research in Angewandte Chemie, International Edition on August 2 ,2021. The article was titled 《Asymmetric Alkoxy- and Hydroxy-Carbonylations of Functionalized Alkenes Assisted by β-Carbonyl Groups》.Category: alcohols-buliding-blocks The article contains the following contents:
As a fundamental type of carbonylation reaction, the alkoxy- and hydroxy-carbonylation of unsaturated hydrocarbons constitutes one of the most important industrial applications of homogeneous catalysis. However, owing to the difficulties in controlling multi-selectivities for asym. hydrocarbonylation of alkenes, this reaction is typically limited to vinylarenes and analogs. In this work, a highly efficient asym. alkoxy- and hydroxy-carbonylation of β-carbonyl functionalized alkenes was developed, providing practical and easy access to various densely functionalized chiral mols. with high optical purity from broadly available alkenes, CO, and nucleophiles (>90 examples, 84-99% ee). This protocol features mild reaction conditions and a broad substrate scope, and the products can be readily transformed into a diverse array of chiral heterocycles. Control experiments revealed the key role of the β-carbonyl group in determining the enantioselectivity and promoting the activity, which facilitates chiral induction by coordination to the transition metal as rationalized by DFT calculations The strategy of utilizing an innate functional group as the directing group on the alkene substrate might find further applications in catalytic asym. hydrocarbonylation reactions. In the experiment, the researchers used ((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-3a-yl)methanol(cas: 20880-92-6Category: alcohols-buliding-blocks)
((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-3a-yl)methanol(cas: 20880-92-6) is a useful reactant for examining the effectiveness of sulfamate and sulfamide groups for the inhibition of carbonic anhydrase-II (CA-II). And it is used as chiral auxiliaries in Michael and Aldol addition reactions.Category: alcohols-buliding-blocks
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts