Cyclohexanediol, cis

The preparation of Pans-1,2-cyclohexanediol by oxidation of cyclohexene with peroxyformic acid and subsequent hydrolysis of the diol monoformate has been described, and other methods for the preparation of both cis- and trans-l,2-cyclohexanediols were cited. Subsequently the trans diol has been prepared by oxidation of cyclohexene with various peroxy acids, with hydrogen peroxide and selenium dioxide, and with iodine and silver acetate by the Prevost reaction. Alternative methods for preparing the trans isomer are hydroboration of various enol derivatives of cyclohexanone and reduction of Pans-2-cyclohexen-l-ol epoxide with lithium aluminum hydride. cis-1,2-Cyclohexanediol has been prepared by cis hydroxylation of cyclohexene with various reagents or catalysts derived from osmium tetroxide, by solvolysis of Pans-2-halocyclohexanol esters in a manner similar to the Woodward-Prevost reaction, by reduction of cis-2-cyclohexen-l-ol epoxide with lithium aluminum hydride, and by oxymercuration of 2-cyclohexen-l-ol with mercury(II) trifluoro-acetate in the presence of ehloral and subsequent reduction. ... 

Organometallic reagents and catalysts continue to be of considerable importance, as illustrated in several procedures CAR-BENE GENERATION BY a-ELIMINATION WITH LITHIUM 2,2,6,6-TETRAMETHYLPIPERIDIDE l-ETHOXY-2-p-TOL-YLCYCLOPROPANE CATALYTIC OSMIUM TETROXIDE OXIDATION OF OLEFINS PREPARATION OF cis-1,2-CYCLOHEXANEDIOL COPPER CATALYZED ARYLA-TION OF /3-DICARBONYL COMPOUNDS 2-(l-ACETYL-2-OXOPROPYL)BENZOIC ACID and PHOSPHINE-NICKEL COMPLEX CATALYZED CROSS-COUPLING OF GRIG-NARD REAGENTS WITH ARYL AND ALKENYL HALIDES 1,2-DIBUTYLBENZENE. 

The addition of B2C14 to multiple bonds was shown to be stereoselective. The initial diborane products isolated after the addition of B2C14 to cis- and trans-2-butene were oxidized to yield meso- and racemic-2,3-butanediols, respectively.478 480 A similar treatment of the addition product of cyclohexene resulted in cis-1,2-cyclohexanediol 480 These observations are consistent with syn addition and the involvement of four-center transition state 42. Similar studies with addition... 

Gamble, R. G., Rutledge, P. S. Stereoselective hydroxylation with thallium(l) acetate and iodine trans- and cis-1,2-cyclohexanediols. Org. Synth. 1980, 59, 169-176. 

In a cis 1,2-cyclohexanediol, one OH is equatorial and the other is axial. Because both cis 1,2-diols (A and E) are cleaved, we know that the cyclic intermediate can be formed when the OH groups are in these positions. In a trans 1,2-diol, both OH groups are equatorial or both are axial (Section 2.14). Two of the trans 1,2-diols can be cleaved (B and C), and one cannot (D). We can conclude that the one that cannot be cleaved must have both OH groups in axial positions because they would be too far from each other to form a... 

These mirror images are actually identical and superimposable on each other. On closer inspection one half of the compound is superimposable on its other half. This is equivalent to saying that there is a plane of symmetry in the compound. Cis-1,2-cyclohexanediol is a meso compound and is not resolvable, although it contains two chiral carbons. 

CIS-1,2-Cyclohexanediol, 257 Cyclohexanone oxime, 2 Cyclohexene, 276 2-Cydohexene-l-ol, 62, 63 CyclohexentHics, 24, 105 Cydohexylnittile, 236 Cyclohexyl trifluoroacetate, 281... 

Carbon NMR spectrum of cis-1,2-cyclohexanediol in deuteriochloroform at 75 MHz Figure 6.4. Continued. 

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