366014-14-4Relevant articles and documents
Radical Trifluoroacetylation of Alkenes Triggered by a Visible-Light-Promoted C–O Bond Fragmentation of Trifluoroacetic Anhydride
Zhang, Kun,Rombach, David,N?tel, Nicolas Yannick,Jeschke, Gunnar,Katayev, Dmitry
, p. 22487 - 22495 (2021)
We report a mild and operationally simple trifluoroacylation strategy of olefines, that utilizes trifluoroacetic anhydride as a low-cost and readily available reagent. This light-mediated process is fundamentally different from conventional methodologies and occurs through a trifluoroacyl radical mechanism promoted by a photocatalyst, which triggers a C?O bond fragmentation. Mechanistic studies (kinetic isotope effects, spectroelectrochemistry, optical spectroscopy, theoretical investigations) highlight the evidence of a fleeting CF3CO radical under photoredox conditions. The trifluoroacyl radical can be stabilized under CO atmosphere, delivering the trifluoroacetylation product with higher chemical efficiency. Furthermore, the method can be turned into a trifluoromethylation protocol by simply changing the reaction parameters. Beyond simple alkenes, this method allows for chemo- and regioselective functionalization of small-molecule drugs and common pharmacophores.
Highly enantioselective copper(i)-catalyzed conjugate addition of 1,3-diynes to α,β-unsaturated trifluoromethyl ketones
Sanz-Marco, Amparo,Blay, Gonzalo,Mu?oz, M. Carmen,Pedro, José R.
supporting information, p. 8958 - 8961 (2015/05/27)
The conjugate diynylation of α,β-unsaturated trifluoromethyl ketones is carried out in the presence of a low catalytic load (2.5 mol%) of a copper(i)-MeOBIPHEP complex, triethylamine and a terminal 1,3-diyne. Pre-metalation of the terminal 1,3-diyne with stoichiometric or higher amounts of dialkylzinc reagent is not required. The corresponding internal diynes bearing a propargylic stereogenic center are obtained with good yields and excellent enantioselectivities. This journal is
Highly efficient asymmetric epoxidation of electron-deficient α,β-enones and related applications to organic synthesis
Zheng, Changwu,Li, Yawen,Yang, Yingquan,Wang, Haifeng,Cui, Haifeng,Zhang, Junkang,Zhao, Gang
supporting information; experimental part, p. 1685 - 1691 (2011/02/25)
The asymmetric epoxidation of electrondeficient olefins has been achieved using inexpensive and readily available prolinols as catalysts with good to excellent yields and enantioselectivities. The utility of the resulting chiral epoxides was illustrated b