Transition-metal-catalyzed addition of heteroatom-hydrogen bonds to alkynes.

In organic molecules carboxylic acid groups are among the most common functionalities Activated derivatives of carboxylic acids have long served as versatile connection points in derivatizations and in the construction of carbon frameworks In more recent years numerous catalytic transformations have been discovered which have made it possible for carboxylic acids to be used as building blocks without the need for additional activation steps A large number of different product classes have become accessible from this single functionality along multifaceted reaction pathways The frontispiece illustrates an important reason for this: In the catalytic cycles carbon monoxide gas can be released from acyl metal complexes, and gaseous carbon dioxide from carboxylate complexes, with different organometallic species being formed in each case Thus, carboxylic acids can be used as synthetic equivalents of acyl, aryl, or alkyl halides, as well as organometallic reagents This review provides an overview of interesting catalytic transformations of carboxylic acids and a number of derivatives accessible from them in situ It serves to provide an invitation to complement, refine, and use these new methods in organic synthesis

Carboxylic acids as substrates in homogeneous catalysis.

Ruthenium-Catalyzed Reactions for Organic Synthesis.

Converting carbon dioxide into carbamato derivatives.

The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are key activation intermediates, have proved extremely useful for many alkyne transformations. They have contributed to the rational design of new catalytic reactions. This 20th anniversary is a suitable occasion to present the advancement of organometallic vinylidenes and allenylidenes in catalysis.

Metal vinylidenes and allenylidenes in catalysis: applications in anti-Markovnikov additions to terminal alkynes and alkene metathesis.

Regioselective synthesis of isopropenyl esters by ruthenium catalysed addition of N-protected amino-acids to propyne

Novel syntheses of oxamides, oxamates and oxalates from diisopropenyl oxalate

Acetylene in Catalysis: a One-step Synthesis of Vinylcarbamates with [RuCl2(norbornadiene)]n

Diisopropenyl oxalate, obtained by catalytic addition of oxalic acid to propyne, is a useful reagent for the access to a variety of α-dicarbonyl compounds such as oxamides, oxamates and oxalates, under very mild conditions.

Serge Lecolier

Papers

Regioselective synthesis of isopropenyl esters by ruthenium catalysed addition of N-protected amino-acids to propyne

Novel syntheses of oxamides, oxamates and oxalates from diisopropenyl oxalate

Acetylene in Catalysis: a One-step Synthesis of Vinylcarbamates with [RuCl2(norbornadiene)]n

Novel Syntheses of Oxamides, Oxamates and Oxalates from Diisopropenyl Oxalate.

Regioselective Synthesis of Isopropenyl Esters by Ruthenium-Catalyzed Addition of N-protected Amino Acids to Propyne.