Borate, tetrakis -, sodium

Experience in PTC with cationic catalysts showed that, in general, the most suitable compounds have symmetrical structures, are lipophilic, and have the active cationic charge centrally located or sterically shielded by substituents. For anionic catalysis sodium tetraphenylborate fulfills these conditions, but it is not stable under acidic conditions. However, certain derivatives of this compound, namely sodium tetra-kis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB, 12.162) and sodium tetrakis[3,5-bis-(l,l,l,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate (HFPB) are sufficiently stable to be used as PTC catalysts for azo coupling reactions (Iwamoto et al., 1983b 1984 Nishida et al., 1984). These fluorinated tetraphenylborates were found to catalyze strongly azo coupling reactions, some of which were carried out with the corresponding diazotization in situ. 

Amino acids may be determined by measuring the amines obtained after the action of a carboxylase with a specific electrode for amines, which is based on a poly(vinyl chloride) membrane containing sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (166) as ion exchanger and tricresyl phosphate as solvent mediator. LOD was 20 and 50 i-M for tyroxine and phenylalanine, determined as tyramine (5) and phenethylamine (33), respectively364. 

SODIUM TETRAKIS(3,5-BIS(TRIFLUOROMETHYL) PHENYL)BORATE, Na[B(3,5-(CF3)2C6H3)4]... 

Sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArp) (227 mg, 0.243 mol) Water (3 mL, degassed)... 

The easiest reactions are those in which the nucleophile is the gold-activated species. Examples of this are Au(I)-catalyzed carbene and nitrene transfers (equations 142 and 143) that convert olefins into cyclopropanes or aziridines, respectively. In the carbene transfer, ethyl diazoacetate is the source of carbene and the active NHC-gold cationic catalyst is generated by chloride abstraction with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate NaBAT4. The cyclopropanation is competitive with other carbene insertions with active C H or N H bonds present in the substrate. For the aziridinations of olefins, nitrene formation is accomplished by the oxidation of sulfonamides with PhI(OAc)2 and the catalyst of choice is a gold-(I) triflate with a terpyridine ligand. 

A complementary, but less pronounced, increase in cis syri) selectivity is provided when diazoacetates with rather small ester groups and rhodium catalysts with bulky ligands, such as iodorhodium(IIl) porphyrins and mcso-tetrakis(2,4,6-triarylbenzoato)di-rhodium(ll) complexes, are employed. For ethyl 2-alkylcyclopropane-l-carboxylates so obtained, a cisfran.s ratio of 2-4 was typical. Notable cis selectivities have also been achieved in the synthesis of ethyl 2-phenylcyclopropane-l-carboxylate with the catalyst [(r/ -C5H5)Fe(CO)2(THF)][BFJ (cis/trans 5.25, see Section 1.2.1.2.4.2.6.3.1.) and copper catalysts prepared in situ from a copper salt [copper(I) iodide, copper(II) acetate or triflate] and sodium tetrakis(7,8,8-trimethyl-4,5,6,7-tetrahydro-2Ff-4,7-methanoindazolyl)borate (3) cis/ trans 2.1-3.2). °... 

Tsubouchi et al. [4] titrated the potassium complexes of alkylphenol, fatty alcohol and sorbitan monopalmitate ethoxylates with sodium tetrakis(4-fluorophenyl)borate (TFPB) as follows. 

Figure 9.7 Example of a crosslinking agent sodium tetrahydroxyl borate and 5,10,15,20-tetrakis(4-boronylphenyl)porphin.

Transition metal-catalysed methods for carbenoid insertion into C-H bonds remain well documented. The asymmetric intramolecular Cu(II)-catalysed C-H insertion reactions of (i) a-diazo-/ -keto esters and phosphonates and (ii) a-diazo sulfones have been described. One can note that the optimal reaction conditions have been found to be quite similar regardless of the nature of the carbenoid precursor the best conditions featured CUCI2 as Cu(II)-source, bis(oxazoline) (68) as chiral ligand and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (i.e., NaBARF) as additive. Under the so-optimized reaction conditions, each of these carbenoid sources have been eonverted into five-membered cyclopentanone-based derivatives (69), whereas a-sulfonyl diazo esters (70) have led to six-membered cyclic compounds (71), thus featuring a distinct but well-known selectivity. In a related work, the asymmetric C-H insertion cyclization of (70) to (71) has also been achieved under Rh(II)-catalysis, using a combination of Rh2(5-pttl)4 (72) as chiral catalyst and menthyl ester as chiral auxiliary. As already mentioned in the previous section, allene-containing substrates (49) have been shown to undergo an intramolecular C-H insertion process under Rh(II)-catalysis. ... 

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