54781-30-5

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 1073-13-8 4,4-dimethylcyclohexenone 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 

Downstream Products

• 40441-34-7 6-bromo-4,4-dimethylcyclohex-2-en-1-one 
• 63577-30-0 6-chloro-4,4-dimethylcyclohex-2-en-1-one 
• 42117-27-1 6-hydroxy-4,4-dimethylcyclohex-2-ene-1-one 
• 119840-58-3 6-(1'-methyl-2'-phenylseleno)-4,4-dimethyl-2,6-exo-cyclohexadien-1-one 

Relevant academic research and scientific papers

An Electrophilic Trifluoromethylthiolation of Silylenol Ethers and β-Naphthols with Diethylaminosulfur Trifluoride and (Trifluoromethyl)trimethylsilane

An efficient and general trifluoromethylthiolation of silylenol ethers and β-naphthols have been accomplished employing the combination of diethylaminosulfur trifluoride (DAST) and (trifluoromethyl)trimethylsilane (CF3TMS) as source of electrophilic trifluoromethylthio moiety for the synthesis of α-trifluoromethylthiolated carbonyl compounds and β-naphthols in good yields. Important features of this method include wide functional group tolerance and use of readily available DAST/CF3TMS. Potential of the methodology was demonstrated via the synthesis of α-trifluoromethylthiolated (+)-4-cholesten-3-one and naphthoquinone. (Figure presented.).

Preparation of gem-dimethylcyclopropane-fused compounds through sigmatropic rearrangements. On/off-switching of the tautomerization of 3,4-homotropilidene by steric hindrance

Cyclopropanation of 4,8,8-trimethylcycloheptatriene having an ether function at the 3-position by unsubstituted carbenoid addition resulted in a complex mixture mainly due to quick valence tautomerization of the produced 3,4-homotropilidene analogue durin

Differences in rates of Diels-Alder reactions as experimental indicators of synchronous or asynchronous transition states

Assessment of the relative rates of the Diels-Alder reactions of the unsymmetrical diene 2-(trimethylsilyloxy)-1,3-cyclohexadiene (1) and its 6,6- and 5,5-dimethyl analogs 2 and 3 indicated that with symmetrical, ethylenic dienophiles (para-benzoquinone, maleic anhydride and N-phenylmaleimide) the Diels-Alder reaction is almost synchronous, but with tetracyanoethylene and with diethyl acetylenedicarboxylate the addition is sufficiently asynchronous as to lead to different rates of reaction with dimethyl-dienes 2 and 3.

Keto/Enol Epoxy Syeroids as HIV-1 Tat Inhibitors: Structure-Activity Relationships and Pharmacophore Localization

Inhibition of the HIV-1 nuclear regulatory protein tat could potentially yield particularly useful drugs because it functions as an activator of transcription.It has known cellular counterpart, and deletions in the gene destroy the ability of HIV-1 to replicate.We recently reported that a structurally unique class of tat inhibitors, 3-keto/enol 4,5-α-epoxy steroids bearing electron-withdrawing substituents at position 2, specifically inhibit tat-induced gene expresion in virus free transfected SW480 cells.In this paper, we reported on additional SAR (structure-activity relationships)for the steroid series and the localization of the pharmacophore to the A-ring functionality.There is a weak enantioselective preference for the natural steroid stereochemistry and hints of additional SAR in the electron-withdrawing group.Compound 34a is of particular interest in that it inhibits HIV replication in H9 cells at a concentrationequivalent to its inhibitory level in the primary tat assay.

Cross-conjugated compounds: microwave spectrum of 4,4-dimethyl-2,5-cyclohexadien-1-one

4,4-Dimethyl-2,5-cyclohexadien-1-one has been prepared by a three-step reaction from 4,4-dimethyl-2-cyclohexen-1-one.Microwave transitions of the cross-conjugated compound have been measured over extended regions from 11 to 40 GHz.The spectrum is a classical a-type spectrum of a near-prolate top with many interspersed lines presumably originating from excited vibrational states.No internal rotation splitting could be observed.We were able to assign 108 rotational transitions with J-quantum numbers up to 40.The least-squares fit showed a standard deviation of 30 kHz and yielded the three rotational constants, A = 3332.158(13) MHz, B = 1193.07386(52) MHz, C = 1082.21280(45) MHz, as well as all five quartic centrifugal distortion constants from Watson's A-reduction: ΔJ = 0.02149(73) kHz, ΔJK = 1.1008(16) kHz, ΔK = -68.42(32) kHz, δJ = 0.00332(16) kHz, δK = -2.7513(99) kHz (representation IR used).The dipole moment was determined from the Stark shift of the M-components of two transitions and was found to be 4.4522(83) D from 93 measurements.

Efficient Synthesis of Siloxy Dienes from α,β-Unsaturated Ketones

A novel method for the preparation of siloxy dienes has been developed.The reaction system was established by a multivariate screening experiment, where catalysts and solvents were selected according to their principal properties.The best system was lithium bromide-chlorotrimethylsilane-triethylamine in tetrahydrofuran.Optimum experimental conditions were determined by response surface methods.The following substrates were used: 2-butenone, 4-methyl-3-penten-2-one, 4-methoxy-3-buten-2-one, 1-acetylcyclohexene, 2-cyclohexenone, 2-cyclopentenone, 4-phenyl-3-buten-2-one, 4-(4-methoxyphenyl)-3-buten-2-one, and 4,4-dimethyl-2-cyclohexenone.Isolated yields were in the range of 82 - 96percent.

SYNTHESIS OF A MONOCYCLIC ANALOGUE OF BIPOLAROXIN, A PHYTOTOXIN OF FUNGAL ORIGIN

A sequence of three reactions leads to an efficient synthesis of compound 5, a model for a newly discovered phytotoxic metabolite from a plant-pathogenic fungus Bipolaris cynodontis.

A General Method for the Preparation of γ-Substituted Cyclohexenals and Cycloheptenals

A general procedure for the preparation of γ-substituted or β'-unsaturated cycloalkenals is described.Starting from 2-cycloalkenones substituents may be introduced as nucleophiles by 1,4-addition followed by trapping of the regiospecifically generated enolate (86-92percent).Peracid oxidation of the enol silane derivative produces an α-hydroxy ketone which, after protection (70-93percent), is homologated to an enol ether by a Horner-Wittig reaction.Mild hydrolysis of the labile vinylogous acetal produces the aldehydes in good yields (62-75percent).Advantages of this method in comparison to known procedures are discussed as are other unsuccessful approaches to this substitution pattern.

Selective Monohydrogenation of Cross Conjugated Cyclohexadienones with Iron Carbonyls and Water

The cross conjugated cyclohexadienone systems 1, 4a, b and 8 are under mild conditions selectively monohydrogenated with Fe2(CO)9 and water, trapped as iron tricarbonyl dienol complexes 11, 5a, b and 9 and therefore protected against further hydrogenation. - Based on deuterium labelling experiments the mechanism and stereochemistry of this hydrogenation is interpreted via various metal hydrides.A skeletal rearrangement of santonin (1) with Fe2(CO)9 described earlier by other authors does not occur according to these investigations.