Secondary alcohol carbon

The two epoxides have the same configuration (R) at the secondary alcohol carbon, but opposite configurations at the stereogenic center of the epoxide ring. They are diastereomers. 

Whitesell and Minton have synthesized (- )-xylomollin (408), the only trans-fiised iridoid, from the racemic bicyclic diene 409. Control of the stereochemistry was effected in the first step by addition of the glyoxylate 410. The two products were separated and the major one, 411, was reduced with lithium aluminum hydride. Conversion of the primary alcohol to a methyl group, with concomitant inversion of stereochemistry at the secondary alcohol carbon atom was carried out by protection of the primary alcohol function (fert-butyldimethylsilyl), tosylation of the secondary hydroxyl, then removal of the silyl group with formation of an epoxide with inversion, and reduction (LiEtaBH) of the epoxide. The remaining steps are shown in Scheme 36. It remains to point out that isoxylomoUin (412) was produced preferentially, and is indeed formed from xylomollin (408) slowly in methanolic solution. ... 

The stereochemical configuation at the secondary alcohol carbons in glucose is presumably retained during this synthesis. The reaction product has been shown to be optically active from the fact that solutions of C12MG display circular dichroism (CD) with the peak near the frequency of the UV absorption band of the amide group [11]. Few studies of optically active surfactant solutions by CD have been reported. 

A white solid, m.p. 178 C. Primarily of interest as a brominaling agent which will replace activated hydrogen atoms in benzylic or allylic positions, and also those on a carbon atom a to a carbonyl group. Activating influences can produce nuclear substitution in a benzene ring and certain heterocyclic compounds also used in the oxidation of secondary alcohols to ketones. 

Certain aliphatic compounds are oxidised by concentrated nitric acid, the carbon atoms being split off in pairs, with the formation of oxalic acid. This disruptive oxidation is shown by many carbohydrates, e.g., cane sugar, where the chains of secondary alcohol groups, -CH(OH)-CH(OH)-CH(OH)CH(OH)-, present in the molecule break down particularly readily to give oxalic acid. 

Aliphatic hydrocarbons can be prepared by the reduction of the readily accessible ketones with amalgamated zinc and concentrated hydrochloric acid (Clemmensen method of reduction). This procedure is particularly valuable for the prep>aration of hydrocarbons wdth an odd number of carbon atoms where the Wurtz reaction cannot be applied with the higher hydrocarbons some secondary alcohol is produced, which must be removed by repeated distillation from sodium. 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

The slow oxidation of primary alcohols, particularly MeOH, is utilized for the oxidation of allylic or secondary alcohols with allyl methyl carbonate without forming carbonates of the alcohols to be oxidized. Allyl methyl carbonate (564) forms 7r-allylpalladium methoxide, then exchange of the methoxide with a secondary or allylic alcohol 563 present in the reaction medium takes place to form the 7r-allylpalladium alkoxide 565, which undergoes elimination of j3-hydrogen to give the ketone or aldehyde 566. The lactol 567 was oxidized selectively with diallyl carbonate to the lactone 568 without attacking the secondary alcohol in the synthesis of echinosporin[360]. 

Alcohols and alkyl halides are classified as primary secondary or tertiary according to the degree of substitution of the carbon that bears the functional group (Section 2 13) Thus primary alcohols and primary alkyl halides are compounds of the type RCH2G (where G is the functional group) secondary alcohols and secondary alkyl halides are compounds of the type R2CHG and tertiary alcohols and tertiary alkyl halides are com pounds of the type R3CG... 

The type of alcohol produced depends on the carbonyl compound Substituents present on the carbonyl group of an aldehyde or ketone stay there—they become sub stituents on the carbon that bears the hydroxyl group m the product Thus as shown m Table 14 3 (following page) formaldehyde reacts with Grignard reagents to yield pri mary alcohols aldehydes yield secondary alcohols and ketones yield tertiary alcohols... 

It IS often necessary to prepare ketones by processes involving carbon-carbon bond formation In such cases the standard method combines addition of a Gngnard reagent to an aldehyde with oxidation of the resulting secondary alcohol... 

Ketones oxidize about as readily as the parent hydrocarbons or even a bit faster (32). Although the reactivities of hydrogens on carbons adjacent to carbonyl groups are perhaps doubled, the effect is small because one methylene group is missing in comparison to the parent hydrocarbon. Ketones oxidize less readily than similar primary or secondary alcohols (35). 

Other carbon electrophiles which are frequently employed include aldehydes, ketones, esters, nitriles and amides of the type RCONMei. An indirect method of acylation involves the initial reaction of a lithio compound with an aldehyde followed by oxidation of the resulting secondary alcohol to the corresponding acyl derivative. 

The reactivity of various steroid alcohols decreases in the order primary > secondary (equatorial) > secondary (axial) > tertiary. The only systematic investigation relating to the selective protection of steroidal hydroxyl functions has been carried out with the cathylate (ethyl carbonate) group. Since only equatorial hydroxyl groups form cathylates this ester has been used as a diagnostic tool to elucidate the configuration of secondary alcohols. 

Citrate itself poses a problem it is a poor candidate for further oxidation because it contains a tertiary alcohol, which could be oxidized only by breaking a carbon-carbon bond. An obvious solution to this problem is to isomer-ize the tertiary alcohol to a secondary alcohol, which the cycle proceeds to do in the next step. 

CI3CCH2OCOCI, Pyr, 20°, 12 h. The trichloroethyl carbonate can be introduced selectively onto a primary alcohol in the presence of a secondary alcohol. DMAP has been used to catalyze this acylation. ... 

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