Cyclohexene 3-hydroxymethyl

Several mono-carba-oligosaccharidic alpha amylase inhibitors, such as acarbose and its homologs, amylostatins, trestatins, oligostatins, adipo-sins, and so on, have been isolated from cultures of micro-organisms, and considerable interest in the biochemistry and chemistry of this class of inhibitors has been stimulated. The characteristic core-structure for inhibitory action is composed of a trihydroxy(hydroxymethyl)cyclohexene moiety and a 4-amino-4,6-dideoxy-D-glucopyranose moiety, bonded by way of an imino linkage at the allylic position. A similar structural unit has been found in the antibiotic validamycins. 

A direct coupling reaction of cycloalkenylsilanes 329 with a silylated nucleobase 330 promoted by (diace-toxyiodo)benzene in the presence of trimethylsilyl triflate in dichloromethane at room temperature has been reported (Scheme 3.132) [385]. This procedure was applied in the synthesis of a novel carbocyclic cyti-dine derivative having bis(hydroxymethyl)cyclohexene as a pseudo-sugar moiety, which was designed as a potential anti-HIV agent. 

Hydroxy-2-butylbutyric acid lactone, A 16.12 4,5-Bis(hydroxymethyl)cyclohexene, A 23.8,... 

Chiral Alcohols and Lactones. HLAT) has been widely used for stereoselective oxidations of a variety of prochiral diols to lactones on a preparative scale. In most cases pro-(3) hydroxyl is oxidized irrespective of the substituents. The method is apphcable among others to tit-1,2-bis(hydroxymethyl) derivatives of cyclopropane, cyclobutane, cyclohexane, and cyclohexene. Resulting y-lactones are isolated in 68—90% yields and of 100% (164,165). 

Photolysis of pyridazine IV-oxide and alkylated pyridazine IV-oxides results in deoxygenation. When this is carried out in the presence of aromatic or methylated aromatic solvents or cyclohexane, the corresponding phenols, hydroxymethyl derivatives or cyclohexanol are formed in addition to pyridazines. In the presence of cyclohexene, cyclohexene oxide and cyclohexanone are generated. 

Carba-y5-DL-idopyranose (77) was prepared from (readily accessible) (l,2,4/3)-5-(hydroxymethyl)-5-cyclohexene-l,2,3,4-tetrol (75) by hydrogenation over a platinum catalyst, acetylation of the product, and 0-deacetylation. 

Cyclohexanone, 2-hydroxymethyl-ene-, preparation of, 54, 38 reaction with alkylenedithio-tosylates, 54, 37 Cyclohexanone, 2,2-trimethy1-enedithio-, 54, 39 4-CYCLOHEXENE—1,2-DICARBOXYLIC ACID, DIETHYL ESTER, trans-, 50, 43... 

Biological. The pure culture Aspergillus niger biodegraded isophorone to 3,5,5-trimethyl-2-cyclo-hexene-l,4-dione, 3,5,5-trimethylcyclohexane-l,4-dione, (5)-4-hydroxy-3,5,5-trimethyl-2-cyclohex-l-one, and 3-hydroxymethyl-5,5-dimethyl-2-cyclohexen-l-one (Mikami et al, 1981). 

While there are few examples of conjugate additions of either a-oxygen- or a-silyl-stabilized carbanions, Tamao and Posner have reported two hydroxymethyl synthons ["ClfcOH] (246 and 247) which show synthetic promise. Additions with the silicon-based synthon (246) is restricted to 2-cyclohexen-l-ones and work-up requires a successive acid and base procedure that is incompatible with sensitive molecules,188a-b while the tin-based synthon (247) is more versatile and the hydroxyl group is obtained under neutral conditions (Scheme 83).,88c... 

Selective Cyclopropanation of Perillyl Alcohol 1-Hydroxymethyl-4-(1-methylcyclopropyl)-1-cyclohexene... 

CYCLOPROPANECARBOXYLIC ACID, 2,2-DIMETHYL-3- (2-METHYLPROPENYL) -, ESTER with N-(HYDROXYMETHYL)-1-CYCLOHEXENE-l,2-DICARBOXIMIDE. ( )-(E)-... 

Chemical Name D-Glucose, 0-4,6-dideoxy-4-(((lS-(la,4a,5fS,6a))-4,5,6-trihydroxy-3-(hydroxymethyl)-2-cyclohexen-l-yl)amino)-a-D-glucopyranosyl-(l-4)-0-a-D-glucopyranosyl-(l-4)-... 

Indeed, starting from the densely hydroxylated compound 122, formation of stannane 123 and [2,3]-sigmatropic rearrangement under Still s condition easily gave cyclohexene 124, whose hydroboration-oxidation led to protected carbapyranose 125. On the other hand, silylation of the hydroxymethyl moiety and hydration of double bond in... 

Oxo-cyclopentene and 3-oxo-cyclohexene react with diisobutylaluminum benzene-tellurolate to produce diisobutylaluminum 3-phenyltelluro-l-cycloalken-l-olates that condensed with butanal and benzaldehyde. The resulting 3-oxo-2-[(organo)hydroxymeth-yl]-l-phenyltcllurocycloalkanes were converted by 3-chloroperoxybenzoic acid to 3-oxo-2-[(organo)hydroxymethyl]-cycloalkenes2. 

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