Vicinal halo-trifluoromethylation of alkenes

Abstract

Both trifluoromethyl and halide groups are widely found in medicinally and pharmaceutically important compounds and, moreover, organohalides are commonly used as versatile intermediates in synthetic organic chemistry.

Recent advances in transition metal-mediated trifluoromethylation reactions

“…[15][16][17][18] The introduction of a CF 3 group into organic molecules has been quite prominent in the last decade, with some outlining the electronic nature of the recruited reagents, which can be radical, electrophilic or nucleophilic (Scheme 2), while others have focussed on the use of catalysts, the stereoselectivity of reactions, or the type of bonds that are deposited in trifluoromethylation reactions. [19][20][21][22][23][24][25][26][27][28][29][30][31][32] In recent years, numerous reports of trifluoromethylation of hydrocarbons and heteroarenes have appeared using various transition metal complexes. This review aims to paint a comprehensive picture on the various methods involved in transforming metal complexes as catalysts or stoichiometric reagents to selectively functionalize C(sp 3 , sp 2 , and sp)-H/X bonds and also to undergo conventional addition reactions for trifluoromethylations.…”

Radical‐Mediated Hydroperfluoroalkylation of Unactivated Alkenes

“…Trifluoromethanesulfonyl chloride is a very common and commercially available reagent. Its use for the chlorotrifluoromethylation of alkenes [50] was pioneered by Kamigata et al. using metal catalysis, [51–54] a reaction that could also be run under photoredox conditions, [55–61] as well as under classical radical initiation [62] .…”

“…[47][48][49] Trifluoromethanesulfonyl chloride is a very common and commercially available reagent. Its use for the chlorotrifluoromethylation of alkenes [50] was pioneered by Kamigata et al using metal catalysis, [51][52][53][54] a reaction that could also be run under photoredox conditions, [55][56][57][58][59][60][61] as well as under classical radical initiation. Therefore, we decided to employ it for the development of a two-step alkene hydrotrifluoromethylation process.…”

Radical Mediated Hydroperfluoroalkylation of Unactivated Alkenes

“…[43][44][45][46] Trifluoromethanesulfonyl chloride is a very common and commercially available reagent. Its use for the chlorotrifluoromethylation of alkenes [47] was pioneered by Kamigata et al using metal catalysis, [48][49][50][51] a reaction that could also be run under photoredox conditions [52][53][54][55][56][57][58] as well as under classical radical initiation. [59] Therefore, we decided to employ it for the development of a two-step alkene hydrotrifluoromethylation process.…”