Catalyst-Free α-trans-Selective Hydroboration and (E)-Selective Deuterated Semihydrogenation of Alkynyl Sulfones.

Here, we present a straightforward α-trans-selective hydroboration of alkynyl sulfones with NHC-boranes without the need for a catalyst. This reaction is compatible with a wide range of substrates for efficiently producing structurally diverse α-borylated vinyl sulfones in satisfactory yields. The hydride transfer from NHC-borane 2a to alkynyl triflone 1b is studied by density functional theory (DFT) calculations for trans-hydroboration. Moreover, a regiodivergent deuterated semihydrogenation of alkynyl triflones has also been developed using D2O as the deuterium source. A variety of diversity-oriented D-containing vinyl triflones were prepared in good to excellent yields with excellent deuterium incorporation ratios. Synthetic manipulations of the deuterated products are achieved for the conversion into valuable deuterated molecules, indicating the utility of this protocol.

Visible-Light-Initiated Sequential Trifluoromethylation/Remote C(sp3)-H Alkynylation of Vinyl Azides by Radical Relay.

A visible-light-initiated trifluoromethylation/remote aliphatic C-H alkynylation of α-alkyl-substituted vinyl azides using acetylenic triflones as both the trifluoromethyl and alkyne donors is described. The reaction occurred under environmentally benign and radical initiator-free reaction conditions, affording γ-alkynylated trifluoromethyl ketone derivatives with a broad scope of substituents. Mechanistic studies suggested that the reaction is initiated via a triplet-triplet energy transfer between the 4CzIPN catalyst and acetylenic triflone, followed by fragmentation to generate a trifluoromethyl radical and an alkynyl radical.