Work

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

Year: 2024

Type: article

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.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202402688

Authors: Szu‐Han Chen, Yi‐Liang Chen, Chun‐Yu Chen, Chi‐Shiun Wu, Ming‐Der Su, Shih‐Ching Chuang

Institutions: National Yang Ming Chiao Tung University, National Chiayi University, Kaohsiung Medical University

Language: English

Topic: Cyclopropane Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,640

Funder: National Science and Technology Council