Carboxylic‐Acid‐Activated Olefins in Decarboxylative Reactions

Abstract

This Minireview summarizes the application of carboxylic-acid-activated olefins in organic synthesis. The ability of carboxylic acid moiety to increase the electrophilic character of alkenes combined with the possibility to remove it under mild reaction conditions via decarboxylation process allows for the development of new reactivity patterns. These strategies involve mainly cascade reactions consisting of either Michael addition followed by decarboxylation or cycloaddition followed by decarboxylation. New synthetic possibilities provided by these approaches are summarized and discussed within this review article.[a] J.

Visible Light-Driven Reductive Azaarylation of Coumarin-3-carboxylic Acids

“…A decarboxylative Michael reaction based on nucleophilic addition to carboxylic-acid-activated olefins followed by a decarboxylation reaction constitutes a powerful synthetic tool. 9 Recently, we described the first photocatalytic, doubly decarboxylative Giese reaction applicable to a wide range of carboxylic acids. 10 Coumarin-3-carboxylic acids 1 constitute useful acceptors in this reaction, opening access to biologically relevant chroman-2-ones 3 .…”

Enantioselective, Decarboxylative (3+2)-Cycloaddition of Azomethine Ylides and Chromone-3-Carboxylic Acids

“…To achieve this goal, decarboxylative 1,3-dipolar cycloaddition (1,3-DC) between carboxylic-acid-group-activated olefins and azomethine ylides was devised [ 23 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ] ( Scheme 2 ). Decarboxylative reactions constitute a very useful strategy in organic synthesis including stereoselective approaches [ 39 , 40 , 41 , 42 ]. They rely on the application of carboxylic-acid-activated Michael acceptors or donors.…”

Doubly Decarboxylative Synthesis of 4-(Pyridylmethyl)chroman-2-ones and 2-(Pyridylmethyl)chroman-4-ones under Mild Reaction Conditions

“…The Michael reaction [ 1 , 2 , 3 , 4 ] is a very powerful means to accomplish this task, allowing access to various useful building blocks for organic synthesis [ 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. Decarboxylative Michael reactions, where Michael acceptors and donors are activated through the presence of the carboxylic acid moiety, have recently emerged as a very useful strategy to access new reactivities [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. In such a setup, carboxylate moiety serves a double purpose.…”