Fert-Butoxide

When the reaction is run with potassium fert-butoxide in THF at -5°C, one obtains (after hydrolysis) the normal Knoevenagel product (32), except that the isocyano group has been hydrated (16-65). With the same base but with DME as solvent the product is the nitrile (33). When the ketone is treated with 31 and thallium(I) ethoxide in a 4 1 mixture of absolute ethanol and DME at room temperature, the product is a 4-ethoxy-2-oxazoline (34). Since 33 can be hydrolyzed to a carboxylic acid and 34 to an a-hydroxy aldehyde, this versatile reaction provides a means for achieving the conversion of RCOR to RCHR COOH, RCHR CN, or RCR (OH)CHO. The conversions to RCHR COOH and to RCHR CN have also been carried out with certain aldehydes (R = H). 

Potassium /ert-butoxide See Potassium fert-butoxide Acids, etc. 

Benzocyclobutene, Butyllithium, Potassium fert-butoxide Adcock, W. et al., J. Organomet. Chem., 1975, 91, C20... 

Potassimn fert-butoxide See Potassimn ferf-butoxide Acids... 

The regioselective cross-coupling between anions of bromomalonate esters orbromoacetate esters and m-dinitrobenzene proceeds in the presence of copper fert-butoxide to give the 2-substituted product. Without the copper salt, the 4-substituted isomer is the only product (Eq. 9.35).62... 

Potassium fert-butoxide ions, (CH3)3COK, can be generated similarily. 

It was observed that there were only slight differences in composition between the products of the MW and conventionally heated reactions. The greatest change in composition was observed in the reaction of 1-bromooctane with fert-butoxide ion where the percent of the elimination product (the alkene) increased from 5%, under conventional reflux to 14% under MW heating. On the other hand there... 

Deprotonation of the imidazolium salt [HsTIME - KPEels with three equivalents of potassium fert-butoxide produced the free carbene TIME " " (2 ), which was isolated and fully characterized (28). Addition of one equivalent of 2 to [(CH3CN)4Cu](PF6) affords the copper carbene complex [(TIME ")2Cu2](PF6)2 (2 -Cu)... 

A recent method reported for the oxidation of primary aliphatic amines to nitro compounds uses fert-butylhydroperoxide (TBHP) and catalytic zirconium tetra-fert-butoxide in presence of molecular sieves. 

The other way of synthesis of clozapine is from 8-chloro-10,ll-dihydro-5H-dibenzo[b,e]l, 4-diazepin-ll-thione, which is alkylated at the sulfur atom of the dibenzodiazepine ring by 4-nitrobenzylchloride in the presence of potassium fert-butoxide, giving iV-methyl derivative (6.5.8). Reaction of this with A-methylpiperazine gives the desired clozapine (6.5.7) [59]. 

The preparations of aryl sulfides typically employ aryl halides as starting materials.4 The procedure described here makes use of the ubiquitous class of commercially available phenolic compounds in the form of aryl triflates, which expands the range of readily accessible aryl sulfides. Prior to this disclosure, the use of aryl triflates in a palladium-catalyzed process for the formation of aryl alkyl sulfides was unprecedented.5 This procedure appears to be general with regard to electronically neutral or electron-deficient aryl triflates (Table 1). The yields in Table I correspond to the initially disclosed procedure employing sodium fert-butoxide as the base. Lower yields were obtained with the 4-nitro-... 

Potassium fert-butoxide, 41, 101 in dehydration of formamides to isocyanides, 41, 101... 

Exercise 14-22 Bromobenzene "reacts rapidly with potassium fert-butoxide in (CH3)2SO (methylsulfinylmethane, dimethyl sulfoxide, DMSO) to give fert-butyl phenyl ether ... 

Exercise 14-24 What products would you expect from the reaction of bromoform, CHBr3, with potassium fert-butoxide in fert-butyl alcohol in the presence of (a) t rans-2-butene and (b) c/s-2-butene ... 

In 1997, Kobayashi and colleagues reported the first truly catalytic enantioselective Mannich-type reactions of aldimines 24 with silyl enolates 37 using a novel chiral zirconium catalyst 38 prepared from zirconium (IV) fert-butoxide, 2 equivalents of (R)-6,6 -dibromo-l,l -bi-2-naphthol, and N-methylimidazole (Scheme 13) [27, 28], In addition to imines derived from aromatic aldehydes, those derived from heterocyclic aldehydes also worked well in this reaction, and good to high yields and enantiomeric excess were obtained. The hydroxy group of the 2-hydroxyphenylimine moiety, which coordinates to the zirconium as a bidentate ligand, is essential to obtain high selectivity in this method. 

Sodium 2-Methyl-2-propoxide, see Sodium fert-butoxide, 1661b... 

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