title: Copper-catalyzed synthesis of 2,4-disubstituted allenoates from α-diazoesters.
abstract: A Cu-catalyzed method for coupling α-substituted-α-diazoesters with terminal alkynes to give substituted allenoates is described. Key to the development of a selective method was the recognition that an adventitous base catalyzes the isomerization to form the allenoate product. A plausible mechanism is proposed, based in part on evidence against a mechanism that involves a Cu(I)-acetylide as a low-valent intermediate.
authors.affiliation: Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.
authors.forename: Matthew
authors.initials: M
authors.lastname: Hassink
authors.forename: Xiaozhong
authors.initials: X
authors.lastname: Liu
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Fox
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis*; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007536:Isomerism; D015394:Molecular Structure
chemical_list: D000466:Alkadienes; D001391:Azo Compounds; C006666:azoester; C025947:propadiene; D003300:Copper