Author(s): Doherty S; Smyth CH; Knight JG
Abstract: Alkyne carbonylation is evolving into a powerful and highly versatile strategy for the synthesis of a host of important carbonyl based intermediates, building blocks and monomers. This chapter highlights a number of recent developments in the area of alkyne carbonylation including the discovery of sulfur tolerant catalysts that enable the hydrothiocarbonylation of terminal alkynes, propargyl alcohols and their derivatives as well as the thiocarbonylation of terminal alkynes to afford a multitude of acyclic and heterocyclic sulfur containing products. Other noteworthy transformations and developments that define the carbonylation of alkynes include the intermolecular oxidative hydroxy-, alkoxy- and aminocarbonylation of terminal alkynes to afford 2-alkynoates and amides, maleic acids and their derivatives and furanones as well as products of tricarbonylation, the oxidative alkoxy- and aminocarbonylation of propargyl alcohols, amines and acetates, ynols and ynones to form lactones as well as acyclic and heterocyclic -alkoxy acrylates. These transformations are complimented by their non-oxidative counterparts; the regioselective intermolecular hydroxy- and alkoxycarbonylation of terminal alkynes, propargyl alcohols and halides, -keto alkynes and internal alkynes, to afford a host of acyclic and cyclic -unsaturated acids and esters, the cyclocarbonylation of alkynyols to form five- and six-membered unsaturated lactones and the carbonylative annulation of internal alkynes to generate carbonylated nitrogen- and oxygen-based heterocycles are also described. Tandem, multicomponent and cascade reactions based on alkyne carbonylation are also being developed and will add further diversity to an already valuable transformation.
Keywords: Alkyne carbonylation, hydrochalcogenocarbonylation, thiocarbomylation, regioselective alkoxycarbonylation, cyclocarbonylation, aminocarbonylation, oxidative alkoxy- and aminocarbonylation, tricarbonylation, inter- and intramolecular carbonylative annulation.
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Dr Simon Doherty
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