103455-38-5Relevant academic research and scientific papers
Dehydration-type Ti-Claisen Condensation (Carbonhomologation) of α-Heteroatom-substituted Acetates with Alkyl Formates: Utilization as (Z)-Stereodefined Cross-coupling Partners and Application to Concise Synthesis of Strobilurin A
Nakatsuji, Hidefumi,Kamada, Risa,Kitaguchi, Hideya,Tanabe, Yoo
, p. 3865 - 3879 (2017)
TiCl4?Et3N or ?Bu3N reagent conducted a highly (Z)-stereoselective carbon homologation (dehydration type Ti-Claisen condensation) of alkyl α-heteroatom (halo and sulfonyloxy)-substituted acetates (XCH2CO2R) with alkyl formates (HCO2R) to afford various alkyl β-alkoxy-α-halo or sulfonyloxy-substituted acrylates (24 examples; 51%–91% yield). Stereoretentive Suzuki-Miyaura, Negishi, and Sonogashira cross-couplings using the obtained methyl β-methoxy-α-halo or sulfonyloxy-substituted acrylates proceeded smoothly to produce a variety of β-alkoxy-α-substituted acrylates in moderate to high yield (35 examples; 29%–99% yield). As a successful application, a 3-step straightforward synthesis of strobilurin A was performed utilizing the present reaction sequence (dehydration type Ti-Claisen condensation and Suzuki-Miyaura cross-coupling), wherein the geometry of the three consecutive olefins (2E,3Z,5E) was completely maintained. (Figure presented.).
