Ligand‐Controlled Palladium‐Catalyzed Carbonylation of Alkynols: Highly Selective Synthesis of α‐Methylene‐β‐Lactones. (17th September 2020)

• Record Type: Journal Article
• Authors: Ge, Yao; Ye, Fei; Liu, Jiawang; Yang, Ji; Spannenberg, Anke; Jiao, Haijun; Jackstell, Ralf; Beller, Matthias
• Is Part Of: Angewandte Chemie. Volume 132:Number 48(2020)
• Page Start: 21769
• Page End: 21774
• Publication Date: 2020-09-17
• Subjects: alkynol -- carbonylation -- catalysis -- palladium -- phosphine -- α-methylene-β-lactone; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202006550
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The first general and regioselective Pd‐catalyzed cyclocarbonylation to give α‐methylene‐β‐lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N ‐arylated imidazole (L11 ) in the presence of Pd(MeCN)2 Cl2 as pre‐catalyst. A variety of easily available alkynols provide under additive‐free conditions the corresponding α‐methylene‐β‐lactones in moderate to good yields with excellent regio‐ and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products. Abstract : The advanced Pd/L11 system enables highly regioselective carbonylation of alkynols for synthesis of a wide range of 4‐membered α‐methylene‐β‐lactones.