A (fluor)ry of activity: The transfer of an intact trifluoromethyl group from a hypervalent iodine reagent to an aliphatic alcohol occurs smoothly upon activation by zinc bis(triflimide). This constitutes a straightforward method for the preparation of trifluoromethoxy alkyl derivatives, compounds otherwise difficult to access.

The reaction of the 10-I-3 hypervalent iodine electrophilic trifluoromethylation reagent 1-trifluoromethyl-1,2-benziodoxol-3-(1H)-one (2) with 2,4,6-trimethylphenol, after deprotonation with NaH and in the presence of 18-crown-6 in a polar, nonprotic solvent, affords 1,3,5-trimethyl-2-(trifluoromethoxy)benzene (4) only as a byproduct. Trifluoromethylation occurs preferentially at the ortho- and para-positions of the aromatic core, giving the corresponding trifluoromethylcyclohexadienones 5 and 6. In case the ortho- and/or para-positions are not substituted, the corresponding products of an aromatic, electrophilic substitution are obtained in moderate yield, for example, 2-trifluoromethyl-4-tert-butylphenol (10a) from 4-tert-butylphenol (10).

Schieb mal rüber: Der Transfer einer intakten Trifluormethylgruppe von einem hypervalenten Iodreagens zu einem aliphatischen Alkohol verläuft glatt bei einer Aktivierung durch Zinkbis(triflimid). Dies ist eine einfache Methode zur Synthese von Trifluormethoxyalkyl‐Derivaten, die sonst nur schwer zugänglich sind.

[reaction: see text] A mild protocol for the chemoselective deprotection of aryl methanesulfonates is described. The transformation can be conducted on highly functionalized substrates and renders the methanesulfonate a useful, previously underutilized protecting group for phenols.

A series of phosphorus ligands containing the 5,6,7,8-tetrafluoronaphthalen-1-yl group (NpF 4 ) has been prepared, starting from 1-bromo-5,6,7,8-tetrafluoronaphthalene. The coordination chemistry of diphenyl(5,6,7,8-tetrafluoronaphthalen-1-yl)phosphine (1) with Ir(III), Pd(II), Pt(II), Rh(I), Ir(I), and Au(I) has been investigated, focusing on a possible remote interaction of the fluorine atom at position 8 of the naphthyl group (F 1 ) with the metal center. The Ir(III) complex [IrCp*Cl 2 (1)] ( 12) displays a weak J(P,F 1 ) coupling constant of 8 Hz and no Ir-F 1 interaction. A cationic derivative, the formally coordinatively unsaturated [IrCp*Cl(1)]SbF 6 (13), is generated upon chloride abstraction. For this complex J(P,F 1 ) is 80 Hz and the Ir-F 1 distance is 2.956(2) A ˚. [MCl(η 3 -allyl)(1)] complexes (14, M = Pt; 15, M = Pd) display what is interpreted as a weaker M-F 1 interaction despite corresponding J(P,F 1 ) values of 67 and 98 Hz and M-F 1 distances of 3.069(2) and 2.995(2) A ˚, respectively. Similar considerations apply to the analogous Rh(I) and Ir(I) complexes [IrCl(COD)(1)] ( 18) and [RhCl(COD)( 1)] (19) (J(P,F 1 ) = 62 and 75 Hz and M-F 1 = 3.0744( 14) and 3.0997(8) A ˚, respectively). With the chiral enantiopure ligand (11bS)-4-(5,6,7,8-tetrafluoronaphthalen-1yl)dinaphtho[2,1-d:1 0 ,2 0 -f][1,3,2]dioxaphosphepine (10) analogous complexes were prepared. Ligand 10 is formally a derivative of 1 where the two phenyl groups have been replaced by a BINOL unit. In the case of [PtCl(η 3 -allyl)(10)] ( 16) and [RhCl(COD)( 10)] ( 21) the coupling between F 1 and the NMRactive nuclei 195 Pt and 103 Rh, respectively, was detected in 2D NMR heteronuclear correlation experiments.