Alcohols, primary with tetrabutylammonium

Primary, secondary, and tertiary alcohols react with benzyl chloromethyl ether (BOMCI, bp 53-56 DC/0.Q7 kPa, HAZARD carcinogenic) in the presence of iPr2NEt to give the BOM ethers501 in good yield. If the reaction requires acceleration, some tetrabutylammonium iodide (10 mol%) may be added to the reaction mixture [Scheme 4.280],503... 

Depending on their location on a sugar, sulfonates have very different reactivities. This is apparent, for example, in the behaviour of tosylates. The tosylate of the primary alcohol function can be substituted without difficulty, even in solvents which are not polar or aprotic. Substitution at positions 3 and 4 are only possible in DMF solution. Substitution at position 2 is absolutely impossible. On the other hand, it is often observed without problems at position 2 starting from a triflate or an imidazylate. These reactivity differences clearly appear in the triple substitution reaction of the tris-triflate P-D-galacto 7 J by benzoate (Alais and David 1990). The latter is prepared from the triol in 5 h at 0 C. It reacts quantitatively with tetrabutylammonium benzoate in toluene in 45 min at room temperature to give the D-gluco substitution product at C-4 and C-6. Heating for 1 h at 100 C then leads to the D-manno tribenzoate 74. 

Chen F-E, Li Y-Y, Xu M, Jia H-Q (2002) Tetrabutylammonium peroxydisuUate in oiganic synthesis XIII. A simple and highly efficient one-pot synthesis of nitriles by nickel-catalyzed oxidation of primary alcohols with tetrabutylammonium ptaroxydisubate. Synthesis 13 1804-1806... 

In 2012, Song Cao et al. devised a novel, one-pot, three-component approach for the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles 37 through the cycloaddition of a wide range of primary alcohols 36 with sodium azide and active methylene ketones 22 at 80 °C in the presence of Af-(p-toluenesulfonyl)imidazole (Tslm), tetrabutylammonium iodide (TBAl), and triethylamine (TEA) in DMF/DMSO (Scheme 4.12) [15]. Potassium hydroxide was used as the base for inducing the cycloaddition. The mild reaction conditions, high yields, and one-pot reaction without the necessity to isolate the unstable and hazardous... 

Polymer supported sodium ruthenate is able to catalyze the oxidation of alcohols with iodosobenzene or tetrabutylammonium periodate in CH2CI2.8 It is not clear whether the primary oxidant is ruthenate or perruthenate. 

Coupling of vinyl halides with allylic alcohols.11 Pd(OAc)2 promotes coupling of vinyl halides with primary allylic alcohols in the presence of silver carbonate and tetrabutylammonium hydrogen sulfate. 

The sodium or potassium alkoxide prepared from primary and secondary alcohols and sodium hydride or potassium hydride in THF reacts with 2-(trimethyl-silyi)ethoxymethyl chloride (SEMCl, bp 57-59 PC/1 kPa, HAZARD carcinogenic) to give the SEM ethers in good yield [Scheme 4.304]481 Alternatively, the alcohol can be alkylated with SEMC1 in the presence of f-PrjNEt in dichloro-methane at 4013 C [Scheme 4.305].257,525,555 Conversion of the SEMCl to the corresponding iodide in situ using tetrabutylammonium iodide accelerates the reaction ... 

A fourth type of product, a carbamate RNHCOOR , can be obtained from primary or secondary amines, if these are treated with CO, O2, and an alcohol R OH in the presence of a catalyst. " Primary amines react with dimethyl carbonate in supercritical CO2 (see p. 414) to give a carbamate. " Carbamates can also be obtained from nitroso compounds, by treatment with CO, R OH, Pd(OAc)2, and Cu(OAc)2, " and from nitro compounds. " When allylic amines (R2C=CHRCHRNR 2) are treated with CO and a palladium-phosphine catalyst, the CO inserts to produce the p,y-unsa-turated amides (R2C=CHRCHRCONR 2) in good yields. " Ring-expanded lactams are obtained from cyclic amines via a similar reaction (see also, 16-22). Silyloxy carbamates (RNHC02SiR 3) can be prepared by the reaction of a primary amine with carbon dioxide and triethylamine, followed by reaction with triisopropylsilyl triflate and tetrabutylammonium fluoride. ... 

Hypochlorites are very good oxidizers of alcohols and are frequently selective enough to oxidize secondary alcohols in preference to primary alcohols see equations 288-291). Solutions of sodium hypochlorite in acetic acid react exothermically with secondary alcohols within minutes [693]. Calcium hypochlorite in the presence of an ion exchanger (IRA 900) oxidizes secondary alcohols at room temperature in yields of 60-98% [76 5]. Tetrabutylammonium hypochlorite, prepared in situ from 10% aqueous sodium hypochlorite and a 5% dichloromethane solution of tetrabutylammonium bisulfate, oxidizes 9-fluorenol to fluorenone in 92% yield and benzhydrol to benzophenone in 82% yield at room temperature in 35 and 150 min, respectively [692]. Cyclohexanol is oxidized to cyclohexanone by teit-butyl hypochlorite in carbon tetrachloride in the presence of pyridine. The exothermic reaction must be carried out with due precautions [709]. 

To a solution of the TBDPS ether (180 mg, 0.38 mmol) in THF (4 mL) was added a tetrabutylammonium fluoride solution (1.0 M in THF, 0.76 mL, 0.76 nunol). The resulting yellow solution was stirred at room temperature for 5 h and quenched by addition of a saturated aqueous solution of NH4CI. After removal of THF in vacuo, the aqueous layer was extracted with EtOAc (3x15 mL). The combined organic layers were washed with brine (10 mL), dried (MgSO4), filtered, and concentrated in vacuo. Purification of the residue by flash chromatography eluting with EtOAc/hexane (1 9) afforded the primary alcohol (73 mg, 82%) as a colorless oil. 

Enolphosphate phosphonates derived from perfluoroalkanoylphosphonates have a number of synthetic uses. Reactions of such compounds with nucleophiles such as amines or alcohols in the presence of catalytic amounts of tetrabutylammonium fluoride (tbaf) gave a,j5-unsaturated perfluorocarboxylic acid derivatives, presumably via a ketene type intermediate (equation 94) When a primary amine was employed as the nucleophile a,j -unsaturated amides were formed, which could be converted into fluorinated pyrimidi-nones by treatment with urea. On the other hand, butylcopper(I) reagent reduces such... 

Heating a tertiary alcohol with l-(trimethylsilyl)iniidazole (abbreviated TMSIM. by-product imidazole) at 100 °C accomplishes O-trimethylsilylation even in the presence of a trisubstituled oxirane [Scheme 4.10].Tetrabutylammonium fluoride (TBAP) catalyses the 0-silylation of alcohols with various silazanes, including l-(trimethylsilyI)imidazole, so that silylation takes place at room temperature in DMF [Scheme 4.11]. In the absence of TBAF, no silylation occurs. The use of more hindered silazanes such as the bissilyl derivative of 5,5-dimethyIhy-dantoin allows regioselective TMS or TBS protection of primary hydroxyl groups in the presence of secondary and tertiary ones. Hydrosilanes and disilanes can be used instead of silazanes in TBAF-caialysed protection of primary and secondary alcohols. ... 

Silnikov described a synthetic route to prepare over fourty 5 -triphosphate dinucleotides with modified carbohydrate-phosphate backbones with the general structure shown [65]. This route employed a combination of solution phase synthesis of the nucleoside dimers followed by the introduction of the triphosphate moiety. The dimers were synthesised from the partially protected nucleoside and 3 -0-/)-chlorophenyl-nucleoside phosphate diester in the presence of 2,4,6-triisopropylbenzenesulfonyl chloride and A -Me-imidazole in pyridine. The pyrophosphate was introduced in a stepwise manner by initial deprotection of the primary alcohol followed by reaction with phosphorus oxychloride in pyridine with subsequent addition of the tetrabutylammonium salt of inorganic pyrophosphate in acetonitrile. 

Trimethylsilylation. Primary, allylic, benzylic secondary, hindered secondary, tertiary alcohols, and phenols are efficiently converted into the corresponding trimethylsilyl ethers when treated with neat TMSA and, when necessary, in the presence of a catalytic amount of tetrabutylammonium bromide (TBABr) in over 91% yields. This reaction can be also used to achieve selective protection of primary and secondary alcohols in the presence of tertiary ones. 

Freedman and Dubois [ 1 ] have found that a variety of ethers can be prepared by the reaction of either primary or secondary alcohols with inexpensive primary alkyl chlorides in the presence of excess concentrated aqueous sodium hydroxide solution and tetrabutylammonium hydrogen sulfate as catalyst. The formation of -butyl n-hexyl ether is shown in equation 5.1. Typically, the 8 2 displacement reaction was not successful with secondary alkyl halides even under phase transfer conditions. 

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