title: Phosphine catalyst-controlled cycloaddition or dienylation reactions of trifluoromethyl aryl ketones with bis-substituted allenoates.
abstract: A chemoselective phosphine-catalyzed cycloaddition or dienylation reaction between trifluoromethyl-substituted ketones and bis-substituted allenoates was described. Under the catalysis of triarylphosphine, the reaction gave a range of trifluoromethylated tetrahydrofurans with broad substrate tolerance and good to excellent stereoselectivity, while the use of trialkylphosphine switched the reaction pathway to furnish CF3-substituted dienyl tertiary alcohols chemoselectively. Moreover, a preliminary study on the asymmetric version of the reaction was also performed, which represents the first example of a phosphine-catalyzed asymmetric reaction between allenoates and carbonyl compounds.
authors.affiliation: Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032, China.
authors.forename: Hua
authors.initials: H
authors.lastname: Xiao
authors.forename: Zhuo
authors.initials: Z
authors.lastname: Chai
authors.forename: Ri-Sheng
authors.initials: RS
authors.lastname: Yao
authors.forename: Gang
authors.initials: G
authors.lastname: Zhao
mesh_terms: D002384:Catalysis; D061565:Cycloaddition Reaction; D005663:Furans / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D005663:Furans; D006845:Hydrocarbons, Fluorinated; D007659:Ketones; D010720:Phosphines; C044646:phosphine