Carbon-oxygen bond formations

Keywords phenol, carboxylic acid, P205/Si02, ester 

A mixture of 1.42 g (0.01 mol) phosphorus pentoxide and 2.5 g of chromatography grade silica gel was placed in a flask and stirred for 30 min. A mixture of equimolar amounts (5 mmol) of the carboxylic acid and phenol was added. Usually an immediate color change was observed. After stirring for 6 h at the temperature indicated in the Table, methylene chloride (50 mL) was added. The mixture was stirred for 1 min and then filtered. The spent reagent was washed twice with methylene chloride (10 mL). The combined organics were washed with aqueous NaOH solution, water and dried over sodium sulfate, and the solvent was removed under reduced pressure. 

References H. Eshghi, M. Rafei, M. H. Karimi, Synth. Commun., 31, 771 (2001). 

Solvent-free organic Synthesis. Kiochi Tanaka 

Copyright 2003 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 3-527-30612-9 

The anomeric hydrogen abstraction can be obtained by an intramolecular Barton type reaction using hydroxyalkylglycosides in presence of iodine and mercury oxide under irradiation. This methodology is used for the synthesis of anomeric spiroorthoesters [6 and 7 in scheme 3). 

This photocyclization proceeds in a one pot reaction with photolytic cleavage of the intermediate carbone-mercury bond and subsequent hydrogen abstraction through a probable hypoiodite intermediate 6 [15 a]. With secondary alcohols (R = H), the reaction is less efficient than with primary ones (R = H), and mainly undergoes a retention of configuration at the anomeric carbon [15 b] by abstraction of the a-anomeric hydrogen. 

Both reactions are of interest for the synthesis of analogs of a new class of antibiotics called orf/iosomycins [16]. 

Propargyl and allyl ketones can be cyclised into furans using AUCI3 (0.1mol%) in acetonitrile 18 

Highly substituted furans play an important role in organic chemistry, both as key structural units in many natural products and important pharmaceuticals, and as useful building blocks in synthetic chemistry examples of their synthesis using gold catalysis have recently been reported.19 

Carbon-oxygen bonds can also be formed by the intramolecular reaction between an alkyne and an epoxide using 5 mol% AUCI3 in acetonitrile 20,21 

an oxygen nucleophile reacted intramolecularly with the alkynyl triple bond, and another example of this is provided by the synthesis of 2,5-disubstituted oxazoles from 7V-propargylcarboxamides under mild conditions using 5 mol% AUCI3 in acetonitrile 22 

While monitoring the conversion via 1H NMR spectroscopy, an intermediate 5-methylene-4,5-dihydrooxazole could be observed and accumulated up to 95% and this is the first direct and catalytic preparative access to such alkylidene oxazolines. 

Keywords phenol, earboxylie acid, PaOs/SiOi, ester 

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The carbon-oxygen bond formation follows the same pathway. For both nitrogen-carbon and oxygen-carbon bond formation, a competing reaction is 13-hydride elimination (if a hydride is present at the heteroatom fragment), which lowers the yield and the reduced arene is obtained after reductive elimination. Reductive elimination of the C-N or C-0 fragments should be faster than 13-hydride elimination in order to avoid reduction of the aryl moiety. The side-reaction is shown at the bottom of Figure 13.25. 

Carbon-Oxygen Bond Formation Hydroxyl or carboxylate groups can participate in a ring-closure reaction by an intramolecular nucleophilic attack to a generated electrophilic center as already described in Schemes 1 and 3. 

Carbon-Oxygen Bond Formation The cathodic reduction of some nitrocarhonyl compounds in aqueous acidic medium gives the hydroxylamino derivatives that can undergo a ring-closure reaction affording anthrandic compounds or isoxazolones [102-104] (Schemes 70 and 71). 

The anodic oxidation of catechol in the presence of 1,3-dimethylbarbituric acid was carried out in aqueous solution containing sodium acetate in an undivided cell at graphite and nickel hydroxide electrodes [114]. The results did not fit with the expected structure (Scheme 47, path A) but a dis-piropyrimidine was isolated in 35% yield (Scheme 47, path B). It seems that the initial attack of 1,3-dimethylbarbituric acid on the anodically formed o-quinone does not occur through the carbon-oxygen bond formation but rather through the carbon-carbon bond formation, giving rise to the final product via several consecutive reaction steps. 

Carbon-Oxygen Bond Formation Based on Hydrogen Transfer 135... 

The environmentally benign synthesis of lactones has attracted attention because of their importance in natural product chemistry. The oxidative cyclization of diols via carbon-oxygen bond formation is the most well-known approach for the synthesis of lactones [70]. 

This review is a summary of the work done and potential opportunities for inexpensive and easily accessible base catalysts, such as alkaline earth metal oxides and hydroxides, as well as alkali metals and oxides supported on alkaline earth metal oxides. Preparation methods of these materials, as well as characterization of basic sites are reported. An extensive review of their catalytic applications for a variety of organic transformations including isomerization, carbon-carbon and carbon-oxygen bond formation, and hydrogen transfer reactions is presented. 

C. Carbon- Oxygen Bond Formation Reactions C.l. Cyanoethylation of Alcohols... 

A criss-cross flexibility of O2 in such a complex was reported" previously by Bartlett and coworkers. Carbon-oxygen bond formation and C—H bond breaking would then follow such an intermediate. Since the formation of the C—Oa bond requires a closer approach to the olefin than the C—H bond breaking, a transition state favouring C—Oa... 

The Tsuji-Trost-type reaction is applicable to bifunctional vinyl epoxide 144 and 1,3-diketone using a palladium catalyst as demonstrated by Koizumi, who obtained polymer 145 (Equation (67)). The reaction proceeds at 0 °C to a reflux temperature of THE. The resulting polymer 145 is isolated in a quantitative yield. The molecular weight of 145 is ca. 3000 (PDI = 2.0-2.7) when 5 mol% of Pd(PPh3)4 is employed as a catalyst. Use of Pd2(dba)3 with several bidentate phosphines such as dppe, dppp, dppb, and dppf is also effective for the polymerization reaction. Propargyl carbonate 146 also reacts with bisphenols in the presence of a palladium catalyst to afford polyethers 147 via carbon-oxygen bond formation at s - and r/) -carbon atoms (Equation (68)). 

These occur readily between electron-rich alkenes and electron-poor carbonyl compounds. The first example, reported in 1959 (64HC(19-2)729), was the formation of 4,4-diaryloxetane-2,2-dicarbonitriles by the room temperature reaction of 1,1-diarylethylenes and carbonyl cyanide. Continued investigation of this reaction shows that a telomerization product is also formed, the tetraphenylpentadienedinitrile (55) from 1,1-diphenylethylene and carbonyl cyanide. This may be interpreted to indicate that carbon-carbon bond formation may commence somewhat ahead of carbon-oxygen bond formation (75MI51302). This... 

The formation of oxygen heterocycles through carbon-oxygen bond formation was also reported. Substituted 2-(o-halophenyl)-ethanols were converted to dihydrobenzofuranes using palladium and Buchwald s bulky biaryl-type ligands (3.43.). The reaction was also efficient in the formation of six and seven membered oxygen heterocycles.53... 

Examples of the transition metal catalyzed formation of carbon-heteroatom bonds other than carbon-nitrogen are less abundant. In a recent survey of the copper catalyzed carbon-oxygen bond formation between alcohols and organotrifluroborates the coupling of 3-thienyltrifluoroborate and 2-furfuryl alcohol gave the expected thienyl-furfuryl-ether in good yield (6.83.),113... 

Promising examples of the catalytic asymmetric Darzens condensation, which yields an epoxide product via carbon-carbon and carbon-oxygen bond formation, have been reported recently by two groups (Scheme 10.11). Toke and co-workers used crown ether 24 in the reaction to form the a,P-unsaturated ketone 78 [38b] with 64% ee, whereas the Shioiri group used the cinchona-derived salt 3a [52], which resulted in 78 with 69% ee. The latter authors propose a catalytic cycle involving generation of a chiral enolate in situ from an achiral inorganic base... 

If we consider reaction of mesylate ion with methyl bromide, we find that this is an endergic reaction thus the transition state lies along the reaction coordinate farther toward the products titan the reactants (Figure 5.11). The activated complex will therefore have a structure more resembling the products. There will be significant carbon-oxygen bond formation between the mesylate group and carbon and only a weak residual bond between carbon and bromine. The bromine... 

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