Synthesis of α-allylated α,β-unsaturated carbonyl compounds using vanadium/palladium contemporaneous dual catalysis.
This protocol describes a new approach for the preparation of α-allylated α,β-unsaturated carbonyl compound by chemoselective cross-coupling of propargyl alcohols with allyl carbonates using an unprecedented vanadium/palladium contemporaneous dual catalysis. This process involves 1,3-transposition of propargyl alcohols by an oxyvanadium catalyst to generate vanadium allenoates and the activation of allyl carbonates by a palladium catalyst to generate π-allylpalladium species. These two active intermediates trap each other more rapidly to afford the observed product, rather than being intercepted by the large excess of starting propargyl alcohol. One example for the preparation of this type of α-allylated α,β-unsaturated carbonyl compound is included in the text. It takes ~20 h to complete the protocol: 1.0 h to set up the reaction, 16 h for the reaction and 2.0 h for isolation and purification. This chemistry has been applied to obtain a wide range of α-allylated α,β-unsaturated ketones, esters and amides, which are highly valuable building blocks in organic synthesis.
Department of Chemistry, Stanford University, Stanford, California, USA. bmtrost@stanford.edu
Barry M
BM
Trost
Xinjun
X
Luan
D000480:Alkynes / Q000737:chemistry; D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000577:Amides / Q000138:chemical synthesis; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis; D007659:Ketones / Q000138:chemical synthesis; D055601:Organic Chemistry Phenomena; D010165:Palladium / Q000737:chemistry; D020005:Propanols / Q000737:chemistry; D014639:Vanadium / Q000737:chemistry
D000480:Alkynes; D000498:Allyl Compounds; D000577:Amides; D002254:Carbonates; D004952:Esters; D007659:Ketones; D020005:Propanols; D014639:Vanadium; D010165:Palladium; C028255:propargyl alcohol