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A palladium iodide catalyzed regioselective carbonylative route to isocoumarin and thienopyranone carboxylic esters
Journal of Catalysis ( IF 7.3 ) Pub Date : 2021-12-01 , DOI: 10.1016/j.jcat.2021.11.028
Raffaella Mancuso 1 , Ida Ziccarelli 1 , Mariangela Novello 1 , Corrado Cuocci 2 , Roberto Centore 3 , Nicola Della Ca' 4 , Diego Olivieri 5 , Carla Carfagna 5 , Bartolo Gabriele 1
Affiliation  

The reactivity of 2-alkynylbenzoic acids under PdI2/KI-catalyzed oxidative alkoxycarbonylation conditions, with oxygen (from air) as external oxidant and an alcohol as external nucleophile, has been studied. It was found that substrates with triple bond substituted with a bulky alkyl group, such as tert-butyl, selectively underwent a 6-endo-dig cyclization - alkoxycarbonylation pathway with ethanol or isopropanol as nucleophile, to give high value added isocoumarin-4-carboxylic esters in good to high yields (67–87%).

When applied to alkynylthiophencarboxylic acids bearing an internal triple bond, the reaction turned out to be completely regioselective toward the formation of the corresponding alkyl thienopyranonecarboxylates ensuing from 6-endo-dig cyclization-alkoxycarbonylation, regardless the nature of the substituent on the triple bond and the external alcohol (54–91% yields).

To confirm the structure of the products deriving from different kinds of substrates, and therefore to corroborate the proposed mechanistic pathways, the crystalline structures of 11 new compounds have been resolved by XRD analysis.



中文翻译:

碘化钯催化异香豆素和噻吩并吡喃酮羧酸酯的区域选择性羰基化途径

已经研究了 2-炔基苯甲酸在 PdI 2 /KI 催化氧化烷氧基羰基化条件下的反应性,氧气(来自空气)作为外部氧化剂,醇作为外部亲核试剂。发现三键被大烷基取代的底物,如丁基,以乙醇或异丙醇为亲核试剂,选择性地进行6--环化-烷氧基羰基化途径,得到高附加值的异香豆素-4-羧酸酯的产率很高(67-87%)。

当应用于带有内部三键的炔基噻吩羧酸时,无论三键上取代基的性质如何,该反应对形成相应的噻吩并吡喃酮羧酸烷基酯具有完全的区域选择性,由 6--环化-烷氧基羰基化产生。外部酒精(54-91% 的产率)。

为了确认来自不同种类底物的产物的结构,从而证实所提出的机理途径,11 种新化合物的晶体结构已通过 XRD 分析得到解析。

更新日期:2021-12-17
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