Aryl-BIAN-ligated silver(i) trifluoromethoxide complex

Abstract

A reaction of acetonitrile-solvated AgOCF3 with 1 equiv. of Aryl-BIAN ligand in THF at room-temperature afforded the silver(i) complex (Aryl-BIAN)AgOCF3 (1) in 75% yield. The crystal structure of this silver(i) trifluoromethoxide was determined by single-crystal X-ray crystallography. The molecular structure of 1 shows the metal centre bound to one molecule of BIAN, one trifluoromethoxide and one THF solvate, resulting in a distorted tetrahedral silver. Density functional theory (DFT) calculations and the natural bond orbital (NBO) analysis were conducted to give insights into the electronic structure of 1 and the bonding characters of the OCF3 group. The reactivity of 1 towards trifluoromethoxylation of organic halides was also examined; a reaction with benzyl bromides gave the desired products of benzyl trifluoromethyl ethers in good to excellent yields.

Facile Access to AgOCF3 and Its New Applications as a Reservoir for OCF2 for the Direct Synthesis of N−CF3, Aryl or Alkyl Carbamoyl Fluorides

“…To this end, we subjected our AgOCF 3 stock solution to benzyl bromides and an alkyl iodide at room temperature for 12 h. The corresponding substitution reactions proved to be highly efficient independently of the substitution pattern of the reactant ( ortho , meta or para ), see Figure A ( 2 a–2 e ). Unlike to previously reported by‐products in substitution reactions with trifluoromethoxy anions, we did not observe any considerable amount of fluorinated by‐products. This suggests that our practical preparation of AgOCF 3 at room temperature has no adverse impact on reactivity or stability; in fact, AgOCF 3 appears to be stable in the reaction medium even for extended periods of time.…”

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

“…Indeed, when [(SIPr)CuCl] or [(SIPr)AuCl] (see Scheme 12,left) was treated with AgOCF 3 (prepared from TFMT) at À30 8C, the desired complex was isolated, and crystal data could be collected. [58] This complex was prepared in 75 % yield from AgOCF 3 (from TFMT) and a bis(arylimino)acenaphthene (Aryl-BIAN, 1 equiv) at room temperature, and was used for the trifluoromethoxylation of benzyl bromides. Furthermore, the silver analogues were found to be even more sensitive than the copper ones as the addition of SIPr as well as 1,10-phenanthroline led to decomposition.…”

“…With the less bulky NHC ligand SIMes (1,3-dimesitylimidazolin-2-ylidene), the corresponding complexes could be formed in situ, but isolation failed. [58] The presence of benzyl chloride, however, was detrimental to the trifluoromethoxylation process. [57] To this day, these complexes have not been implied in trifluoromethoxylation reactions even though a well-defined silver(I) trifluoromethoxide complex was finally synthesized in 2015.…”

Rapid Dehydroxytrifluoromethoxylation of Alcohols

“…After the pioneering work on Ag-mediated (Chen et al., 2015b, Huang et al., 2011, Zha et al., 2016) and Pd-catalyzed (Chen et al., 2015a) trifluoromethoxylation, a breakthrough in transition-metal-promoted approaches was reported recently by Tang, who described a Ag-catalyzed asymmetric intermolecular bromotrifluoromethoxylation of alkenes with trifluoromethylarylsulfonate (TFMS) (Guo et al., 2017). The need for a hazardous agent, CF 3 OX (X=F, Cl, etc.…”