Spirocyclopropanes and Substituted Furans by Controlling Reactivity of 1,3-Enynoates: γ- and δ-Addition of Phosphines to Conjugate Acceptors

Abstract

In the Morita-Baylis-Hillman (MBH) reaction, a nucleophile undergoes β-addition to activated alkenes or alkynes, forming reactive intermediates for subsequent carbon-carbon or carbon-hetero bond formation. By using a π-conjugated acceptor, however, an unprecedented reactivity of 1,3-enynoates and indane-1,3-diones was uncovered in the presence of phosphines. When indan-1,3-diones were used, γ-addition of phosphines to 1,3-enynoates was observed for the first time; moderate to good yields were obtained for 14 substances containing the prominent spirocyclopropane scaffold with 100 % retention of (Z)-alkene. When 2-methyl-indan-1,3-diones were used, di(tri)-substituted furans were produced through the δ-addition pathway, with 20 substances and a yield of up to 88 % being achieved. Control experiments and density functional theory calculations were conducted to obtain insights into the unconventional γ-addition reaction pathway.

Keywords: Enynoate; Indandione; Phosphine; γ-addition; δ-addition.