Trifluoromethanesulfonates preparation from ketones

Bis(trimethylsilyl) peroxide, (CH3)3SiOOSi(CH3)3, is prepared from trimethylsilyl chloride, l,4-diaza[2,2,2]bicyclooctane, and Dabco s complex with 2 mol of hydrogen peroxide [127]. It is used alone [228] or in the presence of catalysts such as pyridinium dichromate [236] trimethylsilyl trifluoromethanesulfonate, CF3S03Si(CH3)3 [228, 237] or tris-(triphenylphosphine)ruthenium dichloride, [(C6H5)3P]3RuCl2 [236]. This reagent oxidizes primary alcohols to aldehydes (in preference to the oxidation of secondary alcohols to ketones [236]), ketones to esters or lactones Baeyer-Villiger reaction) [238], and nucleoside phosphites to phosphates [228]. All these oxidations require anhydrous conditions. 

An improved and convenient preparation of pyrimidines and condensed pyrimidines from ketones and nitriles was reported. In the presence of acetonitrile, the cation generated from methyl ethyl ketone with trifluoromethanesulfonic anhydride is trapped by the nucleophile, whereby a resonance-stabilized nitrilium species is formed. A second molecule of nitrile reacts with nitrilium intermediate, and after elimination of triflic acid, cyclization, and loss of a proton, the pyrimidine product was obtained in a useful yield. The formation of pyrimidines is accompanied by a minimum... 

Trimethylsilyl enol ethers can be prepared directly from ketones. One procedure involves reaction with trimethylsilyl chloride and a tertiary amine. This procedure gives the regioisomers in a ratio favoring the thermodynamically stable enol ether. Use of t-butyldimethylsilyl chloride with potassium hydride as the base also seems to favor the thermodynamic product.Trimethylsilyl trifluoromethanesulfonate (TMS triflate), which is more reactive, gives primarily the less substituted trimethylsilyl enol ether (entry 5, Scheme 1.3). The best ratio of less substituted to more substituted enol ether is obtained by treating a mixture of ketone and trimethylsilyl chloride with LDA at Under these conditions, the kinetically preferred... 

The Frasca method for obtaining 1-arylindazoles also involves a C(3)—C(3a) ring closure (67CJC697). It consists in the cyclization of p-nitrophenylhydrazones of ketones and aldehydes with polyphosphoric acid. The Barone computer-assisted synthetic design program has found several new methods for preparing indazoles (79MI40409). The selected method involves the transformation of jV, jV -diphenylhydrazides (596) into 1-phenylindazoles (597) by means of trifluoromethanesulfonic anhydride. The yields vary from 2% (R = H) to 50% (R = Ph). 

Dialkylboron trifluoromethanesulfonates (Inflates) are particularly useful reagents for the preparation of boron enolates from carbonyl compounds, including ketones, thioesters and acyloxazoiidinones. Recentiy, the combination of dicylohexyiboron trifluoromethanesulfonate and triethyiamine was found to effect the enolization of carboxyiic esters. The boron-mediated asymmetric aldoi reaction of carboxyiic esters is particuiariy usefui for the construction of anti p-hydroxy-a-melhyl carbonyl units. The present procedure is a siight modification of that reported by Brown, et ai. ... 

Conductivity measurements have revealed that DMF and carboxylic acid chlorides form salt-like adducts (22) in an equilibrium reaction (equation 12). Such adducts can be prepared either from DMF and acid halides (chlorides and bromides) or from chloromethyleneiminium salts and salts of carboxylic acids. Acyloxyiminium salts (23) can be prepared in the pure state by reacting acid amides with carboxylic acid chlorides in the presence of silver trifluoromethanesulfonate (equation 13). Salts of type (24 equation 14) are regarded as being intermediates in the synthesis of ketones from carboxylic acids and Grignard reagents in the presence of a-chloroenamines as well as in the preparation of acyl halides (F, Cl, Br, I) by action of a-haloenamines on carboxylic acids. ... 

More tractable and potentially useful polyether ketones, incorporating phenylene-carborane-phenylene units, and with properties suitable for high temperature applications, have been prepared by acylation reactions (using trifluoromethanesulfonic acid as both medium and catalyst) between appropriate dicarboxylic acids and phenoxyphenylcarboranes. For example, the polyetherketone 20 (Scheme 3.6), derived from bis(4-phenoxyphenyl)-para-carborane and biphenyl-4,4 -dicarboxylic acid, is essentially amorphous on isolation from trifluoromethanesulfonic acid, but crystallizes when heated above its glass transition temperature (267°C) before hnally melting at about 390 0... 

Excellent results have been obtained by using boron enolates (alkenyloxyboranes or enol borinates), in what is commonly known as a boron-mediated aldol reaction. The boron enolates are prepared easily from the corresponding ketone and a dialkylboron trifluoromethanesulfonate (dialkylboron triflate, R2BOTf) or chloride (R2BCI) and a tertiary amine base. Boron enolates react readily with aldehydes to give, after oxidative work-up of the resulting borinate species, high yields of the desired aldol product (1.58). 

Various pH aqueous solutions (pH = 1-6) of trifluoromethanesulfonic acid were prepared independently, and the model reaction of the silyl enol ether derived from cyclohexanone (2) with benzaldehyde was tested. Six independent experiments were performed (pH = 1, 2, 3, 4, 5, 6). In the pH 5 and 6 solutions, only a trace amount of the product was detected on TLC, the yields were less than 5%, and hydrolysis of 2 was also observed. In the pH 1-4 solutions, the silyl enol ether immediately hydrolyzed to give the original ketone, and no aldol adduct was obtained. From these experiments, the protons that may be produced from the hydrolysis of the lanthanide triflates were found not to be an active catalytic species in the present aldol reaction of silyl enol ethers with aldehydes the pH values of Yb(OTf)3 solutions were measured as 5.90(1.6x 10- M,THF-H20,4 l)and6.40(8.0x 10- M, HjO). 

This triene was prepared via the silylation of ketone 166, and submitted without purification to a DA reaction with bis-activated dienophile 168. The transmitted diene generated from this reaction migrates upon addition of ytterbium(III) trifluoromethanesulfonate, yielding cross-conjugated enone 170. Upon heating in o-dichlorobenzene, an intramolecular DA reaction occurred, generating tricycle 171. Five steps were then required to access the amphilectene 172. 

---