Recent trends in dehydroxylative trifluoro-methylation, -methoxylation, -methylthiolation, and -methylselenylation of alcohols

Abstract

This review studies on the direct dehydroxylative trifluoromethylation, trifluoromethoxylation, trifluoromethylthiolation, and trifluoromethylselenylation of alcohols.

Recent advances in transition metal-mediated trifluoromethylation reactions

“…[12][13][14] Molecules with trifluoromethyl groups represent a unique class of fluorinated compounds that find their utility not only in the academic community but also in their prevalence in a variety of agrochemical and pharmaceutical drugs (Scheme 1). [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.…”

“…12–14 Molecules with trifluoromethyl groups represent a unique class of fluorinated compounds that find their utility not only in the academic community but also in their prevalence in a variety of agrochemical and pharmaceutical drugs (Scheme 1). 15–18…”

Recent progress in reductive carboxylation of C–O bonds with CO2

“…The direct dehydroxylative functionalization of free alcohols has recently become one of the most impactful areas of research in synthetic chemistry because it is an economic, powerful and eco-friendly strategy for the fabrication of various valuable functionalized organic compounds from inexpensive, environmentally benign, and naturally abundant feedstocks without pre-functionalization of starting materials and isolation of intermediates. 10…”

Trifluoromethoxylation of Arynes Using 2,4‐Dinitro‐1‐(trifluoromethoxybenzene) as Trifluoromethoxide Anion Source

“…Concerning direct ways to construct CF 3 O‐carbon bonds, radical trifluoromethoxylation has been well studied on (hetero)aromatics and acetophenone derivatives [7a,d,8] . The direct introduction of the OCF 3 motif via the trifluoromethoxide anion (CF 3 O − ) has been the focus of research for the past decade [7a,e–g] . Many sources of CF 3 O − have been developed and used on different substrates by nucleophilic substitution or metal‐catalyzed reactions [9] .…”