Synthesis carboxylic acids from

Formation of H2 from OH systems 1, 1.2.3.2 In carboxylic acid synthesis from olefins 16, 14.6.1.4... 

Thieno[3,4-d ]isothiazole-4-carboxylic acid synthesis, 6, 1023 Thienoisothiazoles benzisothiazoles from, 6, 172 Thieno[3,4-c]isothiazoles reactions, 6, 1034 synthesis, 6, 1043... 

Use of the relatively small cyclopropane ring drastically reduces the potential for deleterious steric bulk effects and adds only a relatively small lipophilic increment to the partition coefficient of the drug. One of the clever elements of the rolicyprine synthesis itself is the reaction of d,l tranylcypromine (67) with L-5-pyrrolidone-2-carboxylic acid (derived from glutamic acid) to form a highly crystalline diastereomeric salt, thereby effecting resolution. Addition of dicyclohexylcarbodiimide activates the carboxyl group to nucleophilic attack by the primary amine thus forming the amide rolicyprine (68). 

We were interested in applications of the high level of stereocontrol associated with the asymmetric Birch reduction-alkylation to problems in acyclic and heterocyclic synthesis. The pivotal disconnection of the six-membered ring is accomplished by utilization of the Baeyer-Villiger oxidation (Scheme 7). Treatment of cyclohexanones 25a and 25b with MCPBA gave caprolactone amides 26a and 26b with complete regiocon-trol. Acid-catalyzed transacylation gave the butyrolactone carboxylic acid 27 from 26a and the bis-lactone 28 from 26b cyclohexanones 31a and 31b afforded the diastereomeric lactones 29 and 30. ... 

Brossi, A. 1991. Mammalian alkaloids Conversion of tetrahydroisoquinoline-1-carboxylic acids derived from Dopamine. Planta Medica, 57 S93-S100 and, Xe, X. S., Tadic, D Brzostowska, M Brossi, A., Bell, M. and Creveling, C. 1991. Mammalian alkaloids - Synthesis and O-methylation of (S)-3 -hydroxycoclaurine and R-3 -hydroxycoclaurine and their N-methylated analogs with S-adenosyl-L-[methyl-C-14]methionine in presence of mammalian catechol O-methyltransferase. Helvetica Chimica Acta, 74 1399-1411. 

D. Abbott and H. Weigel, Studies on dextrans and dextranases. Part V. Synthesis of the three carboxylic acids derived from methyl /1-maltoside, J. Chem. Soc., (1965) 5157-5162. 

Hydrazinodiiazole carboxylic acids, synthesis of, from n-bromoacetoacetic ester aiyihydrazones and thioamides, 206... 

We have seen (Sec. 18.5) that in the carboxylic acids obtained from fats we have available long straight-chain units for. .se in organic synthesis. Reduction of these acids to alcohols (either directly or as esters) is a fundamental step in the utilization of these raw materials, since from the alcohols, as we know, a host of other compounds can be prepared (Sec. 16.10). Although only acids of even carbon number are available, it is possible, of course, to increase the chain length and thus prepare compounds of odd carbon number. (For an alternative source of alcohols both of even and odd carbon number, see Sec. 32.6.)... 

Adducts (6) and (7) from amides and chlorophosphoric acid aiyl esters or dichlorophosphoric acid aryl esters respectively are well known. - The adducts are formed in a 1 1 ratio. They have been applied to the synthesis of mixed anhydrides from diarylphosphoric acids and carboxylic acids, as well as mixed substituted esters of pyrophosphoric acid. The adduct formation between primary or secondary carboxamides and dichlorophosphates has been used to prepare nitriles and isonitriles respectively. The adduct from DMF and phenyldichlorophosphate is a useful reagent for the preparation of carboxylic acid esters from the corresponding acids and alcohols, 3-lactams from imines and carboxylic acids," carboxylic acid anhydrides, carboxylic acid esters and thiol esters. Adducts of amides with ester amides or diamides of chlorophosphoric acid have been studied. ... 

With regard to asymmetric synthesis, the possibility that a stereogenic center outside the sigmatropic framework can direct the stereochemical outcome of the electrocyclic process has been intensively exploited recentlyOne method for asymmetric induction has been realized with X representing a chiral carboxylic acid derivative. From the various chiral auxiliaries studied, the C2 symmetrical amide (32) seems to be the most effective, giving via its zirconium enolate) essentially 100% diastereoselectivity and erythro selection, thus permitting ready access to optically active a-hydroxycarboxylic acids (equation 40). 

The entire metabolic pathway of vitamin K has not been elucidated. The major urinary metabolites, however, are glu-curonidc conjugates of carboxylic acids derived from shortening of the side chain. High fecal concentrations are probably due to bacterial synthesis. 

Stoichiometric hydroesterification can be carried out using the zirconium complex [(CsHs)2Zr(H)Cl], as described in Section 4.1.S in the context of carboxylic acid synthesis, and, apart from the use of alcoholic rather than aqueous bromine in the rinal cleavage reaction, the same procedure is applicable (equation 33). ... 

Epoxides - The first indication of the synthetic utility of metalated carboxylic acids resulted from efforts to prepare steroidal aldosterone inhibitors from spiroepoxides.39 Model studies indicated that the reaction fails as a result of severe steric hindrance in either the epoxide or carboxylic acid and that monosubstitution occurs for the same reason.39 The reaction has been used in a key step of an elegant synthesis of vernolepin, 5. 40 Forcing conditions are required, and, in contrast to acid dianions, anions of unactivated esters fail to react with epoxides.39 41... 

Comparing these results with enamide hydrogenation, it is evident that catalysts effecting R amino acid synthesis from enamides direct S-carboxylic acid formation from unsaturated acids. This implies (Scheme 9) that the preferred carboxyl-group configuration is similar in the two series. 

Taylor, S.J.C., D.W. Ribbons, A.M.Z. Slawin, D.A. Widdowson, and D.J. Williams. 1987. Biochemically generated chiral intermediates for organic synthesis the absolute stereochemistry of 4-bromo- s-2,3-dihydroxycyclohexa-4,6-diene-l-carboxylic acid formed from 4-bromobenzoic acid by a mutant of Pseudomonas putida. Tetrahedron Lett. 28 6391-6392. 

Ruthenium(ll)-catalysed reactions of diamines or amino-alcohols have been used to prepare piperidines. A simple synthesis of L-piperidine-2-carboxylic acid (48) from L-lysine (47) has also been reported (Scheme 28). ... 

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