Amines alcohol synthesis

Sulfonates react with a variety of nucleophiles. Synthesis of M A -bis(trifluoro-methyl)aminotnfluoromethanesulfonate and its reactions with nucleophiles were investigated [33] (equation 31) (Table 13). Nucleophilic attack occurs at either nitrogen or sulfur amines give complex mixtures [33]. Polyfluoroalkyl fluorosul-fates react with amines, alcohols, or alkoxides to yield polyfluoroalkyl sulfamates and dialkyl sulfates, respectively [34] (equation 32) (Table 13). In these reactions. 

SCHEME 35- Synthesis of / -D-galactopyranoside precursors, bearing amine, alcohol, and iodide as anchoring functionalities, for metal-based self-assembly.275... 

For the most part, the preparation of monomeric and polymeric carbamates (urethanes), semicarbazides, and ureas consists of condensation reactions of isocyanates with alcohols, hydrazines, or amines. The synthesis of ureas and semicarbazides are described in Chapters 6 and 8, respectively. 

In contrast to cobalt, rhodium permits a one-step oxo alcohol synthesis in the presence of certain monomeric and polymeric amines (8, 9, 10). Included in this group are triethylamine, N-alkylpiperidines, N-methylpyrrolidine, and N,N-dimethylbenzylamine (DMBA). Initial kinetic data on this amine-promoted alcohol synthesis (under severe reaction conditions) have been reported by B. Fell and coworkers (II), but no attempt has been made to characterize the catalytic species in the reaction cycle. 

Reactions have been described for RH = amines, alcohols, aromatics, aliphatics, perfluoroalkyls, hydrogen halides, and thiols (167). Another recent use of S2OfiF2 in organic chemistry has been in the synthesis of lactones by the remote oxidation of carboxylic acids using a... 

The preparation and structures of siloxanediol derivatives has been reviewed29,184 but some representative examples of reactions are given below. Two general methods have been used to make metal siloxides from silanols one involves the direct reaction of a silanol with the metal derivative, usually an amide, alkoxide, halide or alkyl (to give amine, alcohol, HX or alkane byproducts respectively), while the second involves the preparation of a simple alkali metal derivative which can then be used as a siloxide transfer reagent for further synthesis. Only the direct route will be considered here. Two of the most useful siloxide transfer species, (MOPh2Si)20 (M = Li or Na), are... 

When intermediate 81 is formed from indole 80 and l,l -carbonyldiimidazole (GDI) using DMAP to promote indole nitrogen acylation in acetonitrile at reflux, it is reasonably stable, observed by TLC, but not isolated. Treatment of intermediate 81 in situ with amines, alcohols, or thiols afforded the desired derivatives 82. During the reaction of indoles with GDI, some carbonyl diindole 83 was formed. In many cases this material could be isolated and characterized. In an alternative approach, alcohols reacted with GDI stoichiometrically to form an unstable intermediate carbamate species 84, which could in turn be reacted with indoles to form the desired indole-1-carboxylates 82. This new methodology for the formation of compound 82 proved to be useful in one of the approaches for the synthesis of novel Serotonergics. 

Olefin isomerization catalyzed by ruthenium alkylidene complexes can be applied to the deprotection of allyl ethers, allyl amines, and synthesis of cyclic enol ethers by the sequential reaction of RCM and olefin isomerization. Treatment of 70 with allyl ether affords corresponding vinyl ether, which is subsequently converted into alcohol with an aqueous HCl solution (Eq. 12.37) [44]. In contrast, the allylic chain was substituted at the Cl position, and allyl ether 94 was converted to the corresponding homoallylic 95 (Eq. 12.38). The corresponding enamines were formed by the reaction of 70 with allylamines [44, 45]. Selective deprotection of the allylamines in the presence of allyl ethers by 69 has been observed (Eq. 12.39), which is comparable with the Jt-allyl palladium deallylation methodology. This selectivity was attributed to the ability of the lone pair of the nitrogen atom to conjugate with a new double bond of the enamine intermediate. 

Amey, R. L., Martin, J. C. Synthesis and reactions of stable alkoxyaryltrifluoroperiodinanes. A "tamed analog of iodine pentafluoride for use in oxidations of amines, alcohols, and other species. J. Am. Chem. Soc. 1979,101,5294-5299. 

Sulfonyl chlorides (51) are important intermediates in the synthesis of a range of sulfonyl derivatives since the chlorine atom is readily replaced by nucleophilic reagents such as amines, alcohols and hydrazine to give the corresponding sulfonamides (57), sulfonates (58) and hydrazides (59) (Scheme 35). 

Use Preparation of substituted amines and amides, acid anhydrides, esterification of alcohols, synthesis of other organic compounds. 

The catalysts used in alcohol synthesis hold the key to selectivity for methanol, for higher oxygenates, and to the control of hydrocarbon formation. Of interest are the mechanisms and the structure-function relationships in the catalysis of the C-H bond formation in reactions (1) and (2), C-C bond formation in reaction (5), and C-O bond formation in reactions (4), (6) and (7), as well as of reactions utilizing the synthesis intermediates as building blocks for organic syntheses such as amine (refs. 9-11) and aldol (refs. 12-14) syntheses. Further, the mechanistic roles of CO2 and water are of importance to understanding the... 

Table 6.2. Variation of the amines in the 1,3-amino alcohol synthesis by using 4-trifluoromethyl-benzal-dehyde as constant building block...

Amines -> alcohols. A synthesis of secondary alcohols in chiral form from A-Boc secondary amines involves lithiation with the BuLi - (-)-sparteine complex, quenching with RgB, and decomposing the reaction mixture with NaOH-HgOg. ... 

The simplest, and one of the most remarkable, new enzyme mimics has emerged from a piece of lateral thinking by Menger and Fei. [9] No synthesis is involved. These authors simply mixed long-chain carboxylic acids, amines, alcohols and alkylimidazoles, of the sort known to form aggregates, and eventually micelles, in aqueous solution then screened large numbers of such mixtures for catalytic activity. The test reaction was the hydrolysis of the reactive ester 9 (X = O), which is easily followed above pH 7 by the release of the p-nitrophenolate chromophore. Some of the mixtures used effected the hydrolysis of 9 (X = O) at rates too fast to measure manually. Remarkably this was also true in the presence of a single component when this was the hexadecanoate anion, and this system also effects the hydrolysis of the p-nitroanilide (9, X = NH). 

The Reppe alcohol synthesis fi om olefins and CO/H2O with hard iron/amine catalysts can be explained analogously the end products are almost exclusively alco-... 

One of the first works applying this approach was Kimura s synthesis of carboxylic acid-functionalized PHAs (mainly PGA) using the functional glycolide (benzyloxy-carbonyl)methyl-l,4-dioxane-2,5-dione [37]. Since then, this regime has been successfully extended to functionalized lactides offering a way of introducing (protected) functional groups such as protected amine, alcohol, and carboxylic acid [38]. In a similar fashion, Feijen has reported on the synthesis of morpholine-2,5-dione derivatives... 

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