Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates

The copper-catalyzed reductive Ireland-Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diastereomeric anti- and syn-rearranged products, respectively. Copper-catalyzed reductive Ireland-Claisen rearrangement of allylic 2,3-allenoates proceeded effectively only when pinacolborane was used as a reductant to generate various 1,5-dienes in excellent yields and with good diastereoselectivities in some cases. Mechanistic studies showed that the silyl and boron enolates, rather than the copper enolate, underwent a stereospecific rearrangement via a chairlike transition state to afford the corresponding Claisen rearrangement products.

Automated summary

The copper-catalyzed reductive Ireland-Claisen rearrangement led to the synthesis of diastereomeric products with divergent selectivity, utilizing silanes or pinacolborane as reducing agents and triethylphosphite as a ligand. The mechanism studies showed that silyl and boron enolates underwent a stereospecific rearrangement via a chairlike transition state to afford the Claisen rearrangement products.