Unveiling the Chemistry and Synthetic Potential of Catalytic Cycloaddition Reaction of Allenes: A Review

Allenes with two carbon-carbon double bonds belong to a unique class of unsaturated hydrocarbons. The central carbon atom of allene is sp hybridized and forms two sigma-bonds and two pi-bonds with two terminal sp(2) hybridized carbon atoms. The chemistry of allenes has been well documented over the last decades. They are more reactive than alkenes due to higher strain and exhibit significant axial chirality, thus playing a vital role in asymmetric synthesis. Over a variety of organic transformations, allenes specifically undergo classical metal catalyzed cycloaddition reactions to obtain chemo-, regio- and stereoselective cycloadducts. This review briefly describes different types of annulations including [2+2], [2+2+1], [3+2], [2+2+2], [4+2], [5+2], [6+2] cycloadditions using titanium, cobalt, rhodium, nickel, palladium, platinum, gold and phosphine catalyzed reactions along with a mechanistic study of some highlighted protocols. The synthetic applications of these reactions towards the synthesis of natural products such as aristeromycin, ent-[3]-ladderanol, waihoensene(-)-vindoline and (+)-4-epi-vindoline have also been described.

Automated summary

Allenes are a unique class of unsaturated hydrocarbons with two carbon-carbon double bonds. They are highly reactive and exhibit significant axial chirality, making them important in asymmetric synthesis. This review discusses the different types of annulations using metal catalyzed cycloaddition reactions, and also highlights the synthetic applications of these reactions towards natural products.