14618-89-4Relevant articles and documents
Asymmetric Alkoxy- and Hydroxy-Carbonylations of Functionalized Alkenes Assisted by β-Carbonyl Groups
Dong, Kaiwu,Ji, Xiaolei,Ren, Xinyi,Shen, Chaoren,Tang, Lin,Tian, Xinxin,Wang, Zhen
, p. 17693 - 17700 (2021/07/10)
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 asymmetric hydrocarbonylation of alkenes, this reaction is typically limited to vinylarenes and analogues. In this work, a highly efficient asymmetric alkoxy- and hydroxy-carbonylation of β-carbonyl functionalized alkenes was developed, providing practical and easy access to various densely functionalized chiral molecules 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 asymmetric hydrocarbonylation reactions.
Carbonylative coupling of allylic acetates with aryl boronic acids
Ma, Wei,Xue, Dong,Yu, Ting,Wang, Chao,Xiao, Jianliang
supporting information, p. 8797 - 8800 (2015/05/20)
The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd-PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.
Synthesis of α,β-unsaturated ketones by Pd-catalyzed decarboxylative allylation of α-oxocarboxylates
Rodriguez, Nuria,Manjolinho, Filipe,Gruenberg, Matthias F.,Goossen, Lukas J.
, p. 13688 - 13691 (2012/01/15)
A palladium/p-tolylphosphine system has been developed that catalyzes the extrusion of carbon dioxide from α-oxocarboxylic acid allyl esters, leading to α,β-unsaturated ketones (see scheme). The palladium complex activates the substrate and mediates the carbon-carbon bond formation to give allyl ketones, and subsequent double bond shift to the α,β position. The actual decarboxylation step with formation of the acyl nucleophile is promoted by phosphine.
