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RESEARCH PRODUCT
Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes.
Gonzalo BlayAmparo Sanz-marcoM. Carmen MuñozJosé R. Pedrosubject
Trifluoromethyl010405 organic chemistryChemistryStereochemistryConjugate additionOrganic ChemistryEnantioselective synthesisEnonesFluorineGeneral Chemistry010402 general chemistry01 natural sciencesCatalysis0104 chemical sciencesCatalysischemistry.chemical_compoundAlkynylationAlkynesFISICA APLICADAAsymmetric catalysisOrganic chemistryConjugatedescription
The first catalytic enantioselective conjugate alkynylation of α,β-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a CuI-MeOBIPHEP complex (2.5 mol %) and triethylamine (10 mol %) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogenic center at the β position with good yields and excellent enantiomeric excesses in most of the cases. No 1,2-addition products were formed under the reaction conditions. The procedure showed broad substrate scope for alkyne, diyne, and enone. A rationale for the observed stereochemistry has been provided. Finally, the potential application of the reaction products in the synthesis of chiral tetrahydrofurans bearing a trifluoromethylated quaternary stereocenter has been devised.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-06-23 | Chemistry (Weinheim an der Bergstrasse, Germany) |