A New and Direct Trifluoromethoxylation of Aliphatic Substrates with 2,4‐Dinitro(trifluoromethoxy)benzene

Abstract

The reaction of tetrabutylammonium triphenyldifluorosilicate with 2,4-dinitro(trifluorometh-

Oxygen-Bound Trifluoromethoxide Complexes of Copper and Gold

“…2−5 This reactivity is akin to that of trifluoromethanol, which readily loses HF at room temperature. 6 The crystal structure of the [((CH 3 ) 2 N) 3 3 ] salt reveals a short C−O bond length of 1.227(4) Å and elongated C−F bond lengths of 1.390(3) and 1.397(4) Å, which the authors believe is consistent with a negative hyperconjugative effect related to Scheme 1. 7 Despite the tendency of trifluoromethoxide to decompose, important methods to form trifluoromethyl ethers based on the trifluoromethoxide anion have started to emerge.…”

“…Important bond lengths and angles for 2 are shown in Table 3. The carbon− oxygen bond in 2 was determined to be 1.247(7) Å, only slightly longer than the 1.227(4) Å bond observed in [((CH 3 ) 2 N) 3 3 ]. The oxygen−carbon−fluorine bond angles in the gold complex were slightly smaller than those observed in [((CH 3 ) 2 N) 3 3 ].…”

“…The carbon− oxygen bond in 2 was determined to be 1.247(7) Å, only slightly longer than the 1.227(4) Å bond observed in [((CH 3 ) 2 N) 3 3 ]. The oxygen−carbon−fluorine bond angles in the gold complex were slightly smaller than those observed in [((CH 3 ) 2 N) 3 3 ]. The atoms O1, F2, and F3 all possess intermolecular contacts shorter than the sum of the van der Waals radii with hydrogen atoms of adjacent NHC ligands; therefore, some care must be taken in interpreting the bond distances and angles involving the oxygen and fluorine atoms.…”

“…1 The lack of fundamental studies on this group is exacerbated by the fact that the [CF 3 O] anion readily decomposes into fluorophosgene and fluoride, even at low temperatures (Scheme 1). 2−5 This reactivity is akin to that of trifluoromethanol, which readily loses HF at room temperature.…”

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

“…[59] Benzyl bromide could thus be trifluoromethoxylated, and the best reaction conditions entailed the use of TBAT (tetrabutylammonium triphenyldifluorosilicate) as the fluoride source (Scheme 13). [59] Benzyl bromide could thus be trifluoromethoxylated, and the best reaction conditions entailed the use of TBAT (tetrabutylammonium triphenyldifluorosilicate) as the fluoride source (Scheme 13).…”