Cyclohexadiene-trans-diols

Microbially Produced Functionalized Cyclohexadiene-trans-diols as a New Class of Chiral Building Blocks in Organic Synthesis On the Way to Green and Combinatorial Chemistry... 

I 6.4 Microbially Produced Functionalized Cyclohexadiene-trans-diols... 

Lithiated allyl sulfide 256-Li reacted with m-xylylene dibromide 257 to afford the bis-sulfide 258. A double Mislow-Evans rearrangement of 258 and subsequent reductive trapping of the sulfenate ester provided the symmetric trans-diol 255. Monoprotection, Sharpless asymmetric epoxidation, and reductive ring-opening of the epoxide gave 1,3-diol 259 in 97% ee. After several functionalizations, the arene was subjected to Birch reduction to provide 1,4-cyclohexadiene 254. Ozonolysis of the diene, followed by reductive workup and treatment of the resulting 1,3-diketone with acid furnished pyra-... 

Hausmann T, Pietruszka J (2009) Enantiopure dicyclopropanes from trans-cyclohexadiene-diols. Synlett 21 3271-3274... 

A different approach has been used by Nakajima and his coworkers32 in the synthesis of inositols. Their starting materials were the cis- and trans-3,5-cyclohexadiene-l,2-diols (XIII and XV) ( benzeneglycols ) which... 

Demonstration of cis addition with acetylene is unequivocal, in that the stereochemistry of the resulting bis(dihaloboryl)ethylene has been shown directly by spectroscopic evidence (90) and by conversion of the initially produced cis isomer to the trans compound by photochemical isomerization (27). Stereochemical inferences in the olefin addition reactions are based on the assumption that hydrolysis and oxidation of the bis(boryl) compounds to the corresponding diols occurs with retention of configuration, as is the case in closely related systems 19). The NMR spectrum of the addition product of B2CI4 with 1,3-cyclohexadiene is also consistent with cis addition (120). 

The acid-catalysed hydrolysis reactions of vinyl epoxides (140 = 1-4) have been shown to follow an A-l mechanism, via the intermediate allylic cations (141). ° The distributions of products from both (140 = 1) and (140 = 3) were similar, comprising all four possible cis- and trans-1,2- and -1,4-diols, whereas cyclohexadiene oxide (140 = 2) gave mainly the trans-... 

Over 300 diol metabolites are known.8 Several diols and some secondary synthons derived from them have recently become commercially available Eastman Fine Chemicals, Genencor (1 S-cis)-3-Chloro-3,5-cyclohexadiene-1,2-diol, (1 S-cis)-3-bromo-3,5-cyclohexadiene-1,2-diol, (1 S-cis)-3-iodo-3,5-cyclohexadiene-1,2-diol, (5S-cis)-5,6-dihydroxy-1,3-cyclohexadiene-1 -carbonitrile, cis-2R,3S-2,3-dihydroxy-2,3-dihydrobenzonitrile acetonide, (1R-cis)-1,2-dihydro-1,2-naphthalenediol, (1R-cis)-1,2,3,4-tetrahydro-1,2-naphthalenediol, (4S-trans)-4,5-dihydroxy-3-oxo-1 -cyclo-hexene-1-carboxylic acid, furo[3,4-d]-1,3-dioxol-4(3aH)-1 -dihydro-6-hydroxy-2,2-dimethyl-[3aR-(3aa,6aa)]. 

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