Direct Stereoselective β‐Arylation of Enol Ethers by a Decarboxylative Heck‐Type Reaction

Abstract

Despite remarkable advances to promote regio-and stereoselective decarboxylative arylation of inactivated olefins with benzoic acid derivatives, methodologies involving heterosubstituted alkenes are still lacking. Herein, Pd II -catalyzed decarboxylative Heck coupling of α-alkoxyacrylates with (hetero)aryl carboxylic acids for the stereocontrolled production of (Z)--heteroarylated vinyl ethers is reported. This methodology offers a rational and step-economical route to the synthesis of [a]

Sustainable Hydrogenation of Vinyl Derivatives Using Pd/C Catalysts

“…The nucleophilic addition proceeds under superbasic conditions in good yields without the use of gaseous acetylene and can be safely carried out in a laboratory. Labeled compounds with deuterium [21] and carbon 13 C [22] incorporation can also be obtained that increase applications in further transformations: polymerization [23], Heck-like reactions [24], cycloaddition [25,26], and many others. Here, we expand the scope of applications of vinyl derivatives and demonstrate that molecular hydrogen can be successfully added to functionalized vinyl derivatives.…”

Alkyl Enol Ethers: Development in Intermolecular Organic Transformation

“…Likewise, Hoarau and co‐workers reported a Pd(II)‐catalyzed decarboxylative Heck coupling of carboxylic acid 60 with 61 to afford ( Z )‐β‐heteroarylated vinyl ethers 62 in regio‐ and stereocontrolled fashion (Scheme 23). On their observation, electron‐rich aryl carboxylic acid shows a decarboxylation by Pd(II)‐catalyst, while electron‐deficient substrate proceeds via silver(I)‐mediated decarboxylation, (path I and II) as shown in scheme 23 [40] …”

Metal -free PhI(OAc)2-oxidized decarboxylation of propiolic acids towards synthesis of α-acetoxy ketones and insights into general decarboxylation with DFT calculations

“…Moreover, decarboxylative coupling strategies to construct both C–C and C–heteroatom bonds from carboxylic acids have been extensively reported since the late 2000s. 1 The early decarboxylation coupling of carboxylic acids proceeded in situ -position flair and required the participation of transition metals such as Pd, 2 Ag, 3 Cu, 4 Au 5 and Rh 6 to form the corresponding aryl–metal species, 5,7 which subsequently promotes the ongoing transformation. Furthermore, transition metals like Pd 8 and Ru 9 could catalyze the ortho -coupling reaction of carboxylic acids, to realize the functionalization of carboxyl ortho functionals.…”