Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium‐Catalyzed Carbonylation

Abstract

A palladium-catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α-bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late-stage carbon-isotope labeling.

A Broad‐Spectrum Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates**

“…Flash column chromatography was performed on 200-300 mesh silica gel (Huanghai, China). 2-(diphenylphosphanyl)-5-methylbenzenesulfonyl fluoride (1a), [1] 4-methylbenzenesulfonyl fluoride (1c), [2] 4-methoxybenzenesulfonyl fluoride (1e), [2] 2-methylbenzenesulfonyl fluoride (1f), [3] 4-(trifluoromethyl)benzenesulfonyl fluoride (1g), [3] 4-fluorobenzenesulfonyl fluoride (1h), [4] benzenesulfonyl fluoride (1i), [4] 4-(tert-butyl)benzenesulfonyl fluoride (1l), [2] naphthalene-1-sulfonyl fluoride (1m), [2] ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl fluoride (1n), [2] 4-methoxyphenyl fluorosulfate (4b), [5] 4-isopropylphenyl fluorosulfate (4d), [6] 4-iodophenyl fluorosulfate (4e), [7] 3,5-dimethylphenyl fluorosulfate (4f), [8] benzo[d] [1,3]dioxol-5-yl fluorosulfate (4g), [3] phenyl fluorosulfate (4h), [5] phenyl fluorosulfate, [3] 4-bromophenyl fluorosulfate (4i), [9] [1,1'biphenyl]-4-yl fluorosulfate (4j), [3] (8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4n), [10] (8R,9S,13S,14S,17R)-17-ethynyl-17-hydroxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4o), [3] 3-nitrobenzenesulfonyl fluoride (8), [3] 4-(2-(pyrrolidin-1-yl)ethoxy)aniline ( 12), [11] 1H-benzo[d] [1,2,3]triazol-1-yl benzenesulfonate (16), [12] were prepared according to literature procedures. NMR data were in agreement with the literature data.…”

A Broad-Spectrum, Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates

“…Flash column chromatography was performed on 200-300 mesh silica gel (Huanghai, China). 2-(diphenylphosphanyl)-5-methylbenzenesulfonyl fluoride (1a), [1] 4-methylbenzenesulfonyl fluoride (1c), [2] 4-methoxybenzenesulfonyl fluoride (1e), [2] 2-methylbenzenesulfonyl fluoride (1f), [3] 4-(trifluoromethyl)benzenesulfonyl fluoride (1g), [3] 4-fluorobenzenesulfonyl fluoride (1h), [4] benzenesulfonyl fluoride (1i), [4] 4-(tert-butyl)benzenesulfonyl fluoride (1l), [2] naphthalene-1-sulfonyl fluoride (1m), [2] ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl fluoride (1n), [2] 4-methoxyphenyl fluorosulfate (4b), [5] 4-isopropylphenyl fluorosulfate (4d), [6] 4-iodophenyl fluorosulfate (4e), [7] 3,5-dimethylphenyl fluorosulfate (4f), [8] benzo [d] [1,3]dioxol-5-yl fluorosulfate (4g), [3] phenyl fluorosulfate (4h), [5] phenyl fluorosulfate, [3] 4-bromophenyl fluorosulfate (4i), [9] [1,1'biphenyl]-4-yl fluorosulfate (4j), [3] (8R,9S,13S,14S)-13-methyl-17-oxo- 7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4n), [10] (8R,9S,13S,14S,17R)-17-ethynyl-17-hydroxy-13-methyl- 7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4o), [3] 3-nitrobenzenesulfonyl fluoride (8), [3] 4-(2-(pyrrolidin-1-yl)ethoxy)aniline (12), [11] 1H-benzo [d] [1,2,3]triazol-1-yl benzenesulfonate (16),…”

New Directions in Transition Metal Catalyzed Carbonylation Chemistry

“…Screening different pincer ligands based on a pyrrole- [31,32] or followed by addition of two equivalents TMSCF 3 as shown in Scheme 4. [25] 5-Bromopyrimidine or 3,5-dibromopyridine could effectively be transformed to incorporate one or two HFIP groups, respectively, as shown with compounds 22 and 23. Fluorosulfates have recently emerged as reactive coupling partners for cross-couplings or SuFEx click chemistry as introduced by Sharpless.…”

“…Furthermore, instead of employing COgen as the CO source, CO 2 could be exploited in the presence of a disilane and catalytic CsF providing a similar yield of the hexafluoride-containing compound 24 (68%). [28] 13 C-labeling of estrone proved possible by employing 13 COgen (25). The ketone group remained untouched under these conditions, however, having more activated ketone groups present in the starting material allowed for the incorporation of an additional CF 3 group as exemplified with compound 26.…”