Epoxides carboxylates

Alkene Peroxy acid Epoxide Carboxylic acid... 

Allen JR, DD Clark, JG Krumn, SA Ensign (1999) A role for coenzyme M (2-mercaptoethanesulfonic acid) in a bacterial pathway of aliphatic epoxide carboxylation. Proc Natl Acad Sci USA 96 8432-8437. 

Coenzyme M was shown to function as the central cofactor of aliphatic epoxide carboxylation in Xanthobacter strain Py2, an aerobe from the Bacteria domain (AUen et al. 1999). The organism metabolizes short-chain aliphatic alkenes via oxidation to epoxyalkanes, followed by carboxylation to p-ketoacids. An enzyme in the pathway catalyzes the addition of coenzyme M to epoxypropane to form 2-(2-hydroxypropylthio)ethanesulfonate. This intermediate is oxidized to 2-(2-ketopropylthio)ethanesulfonate, followed by a NADPH-dependent cleavage and carboxylation of the P-ketothioether to form acetoacetate and coenzyme M. This is the only known function for coenzyme M outside the methanoarchaea. 

Alkyl halides, alcohols, epoxides, carboxylic acid and its derivatives, and benzene and its derivatives. 

From Phenyl Trimethylsilyl Tellurium and Epoxides, Carboxylic Acid Esters, Ethers, and... 

Unsymmetrical alkyl phenyl tellurium derivatives were prepared in good yields from phenyl trimethylsilyl tellurium and epoxides, carboxylic acid esters, and linear or cyclic ethers under very mild conditions. In these reactions, which proceed in dichloromethane in the presence of a catalytic amount of zinc iodide, a carbon-oxygen single bond is cleaved. The highly nucleophilic benzenetellurolate binds to the carbon fragment, whereas the trimethylsilyl group becomes linked to the oxygen. 

TBA4H6(Fe2- Ni(0Ac)3)PW9037 Alkane Alkene Aldehyde Alcohol, ketone Allylic alcohol, allylic ketone, epoxide Carboxylic acids 02 or h2o2 o2 o2 MeCN 82 °C or 50 °C 30 °C 30 °C 403... 

A full report has been published on the preparation of fused valerolactones from cyclopentadiene anions by condensations with epoxides, carboxylation, and finally cyclization (Scheme 26). Diels-Alder reactions of 3-hydroxy-2-pyrones usually lead to benzene derivatives by decarboxylation of the intermediate lactone. It has now been shown that these lactones can be isolated in good yields by suppression of the CO2 loss by carrying out the cycloadditions under a high pressure of carbon dioxide. 

Scheme 4.19 Homopolymerisation of an epoxide-carboxylic monomer. PMA Propylene glycol monomethyl ether acetate TBABr tetrabutylammonium bromide and TPPB tetraphenylphosphonium bromide [78]...

Figure 8.4 Epoxide carboxylation reaction pathway over Nb O catalyst (a) and role of solvent in the carboxylation of epoxides (b) (adapted from Ref. [32]).

The earlier studies and the competition experiments [5b] with equivalent molar, enal, or enone 9-BBN (3-5% excess) reveal that enals or enones are selectively reduced to allylic alcohols (Eq. 25.9) in the presence of other organic functional groups such as nitro, halogen, epoxide, carboxylic acid, amide, ester, nitrile, sulfide, disulfide, sulfoxide, sulfone, tosylate, azo, etc. 

Here we show a novel methodology for the functionalizations of hydrocarbons, including oxygenation, nitration, sulfoxidation, epoxidation, carboxylation, and oxyalkylation through generation of the catalytic carbon radical. In particular, the NHPI-catalyzed aerobic oxidations of alkanes, which are very important in industry worldwide, are described in detail. 

Ring-opening reaction Epoxide Carboxylic acid, MAn, hydroxyl, amine Ring-opening reaction... 

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