35394-07-1

Upstream product

• 67-56-1 methanol 
• 19980-19-9 4-t-butyl-1-trimethylsilyloxy-1-cyclohexene 
• 4147-00-6 4-tert-butyl-1-(1-pyrrolidinyl)cyclohexene 
• 36336-08-0 methyl hypofluorite 
• 143191-52-0 1,1,2-trimethoxy-4-tert-butylcyclohexane 
• 57466-12-3 4-tert-butyl-1-methoxycyclohexene 
• 98-53-3 4-tercbutyl-cyclohexanone 

Downstream Products

• 68211-39-2 trans 4-tert-butyl-2-methoxymethylene cyclohexane 
• 68211-39-2 cis 4-tert-butyl-2-methoxymethylene cyclohexane 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 145041-49-2 cis-4-t-butyl-1,2-epoxymethano-1-hydroxycyclohexane 
• 145041-49-2 trans-4-t-butyl-1,2-epoxymethano-1-hydroxycyclohexane 

Relevant academic research and scientific papers

π-facial diastereoselection in the 1,2-addition of allylmetal reagents to 2-methoxycyclohexanone and tetrahydrofuranspiro(2-cyclohexanone)

The stereochemical course of the 1,2-addition of several allylmetal reagents and of the Normant Grignard [ClMgO(CH2)3MgCl] to 2-methoxycyclohexanone and tetrahydrofuranspiro-(2-cyclohexanone) has been determined. In four of the six substrates examined, a 4-tert-butyl group is present to serve as a conformational anchor. The neighboring methoxyl substituent is shown to be capable of engaging effectively in chelation, although special circumstances can dictate otherwise. Experiments involving the allylindium reagent as the nucleophile in aqueous solution reveal that the presence of water does not inhibit the operation of chelation control, which often exceeds that attainable with the corresponding magnesium, cerium, and chromium reagents in anhydrous media by significant margins. The extent to which cooperation between the α-oxygen atom and control of π-facial nucleophilic attack reaches a maximum ( > 97:3) is when the system is conformationally rigid and the 2-methoxy and 4-tert-butyl groups are both oriented equatorially. As the steric bulk about the oxygen is increased, the ability of indium to anchor onto the heteroatom is significantly lessened. The results of competition experiments are detailed. The prospects for useful synthetic applications of indium catalysis in water or water/THF mixtures appear to be very promising.

Axial/equatorial proportions for 2-substituted cyclohexanones

Axial-equatorial conformational proportions have been measured for 2- substituted cyclohexanones in chloroform by the Eliel method for F, Cl, Br, I, MeO, MeS, Me2N, MeSe, and Me. For the first seven of these, at least five experimentally independent measurables were used and the resulting conformational preferences appear to be accurate to within 10%. Systematic errors degraded the results for MeSe and Me. For Me2N, the conformational preference also was measured for the first time at slow exchange in the low- temperature 13C spectrum in several solvents. In chloroform, steric and polar effects contribute to the conformational preferences, with steric effects dominant for large groups such as I and MeS.

A novel electrophilic methoxylation (with a little help from F2)

Methyl hypofluorite, MeOF, easily made from MeOH and F2, proved to be an excellent source for the novel electrophilic methoxylium ion "MeO+". MeOF was reacted with the enol forms of carbonyls, producing in good to excellent yields the corresponding α-methoxy carbonyl derivatives. It was found that the methoxylation is best carried out on methyl enol ethers. Silyl enol ethers and enol acetates were also tested but with limited success. The reaction proceeds through an addition elimination mechanism.

Toward the Synthesis of the Taxol C,D Ring System: Photolysis of α-Methoxy Ketones

Model systems for the synthesis of the C and D rings of taxol are described, involving photolyses of α-methoxy ketones.Cis-fused oxetanols common to taxol are formed along with novel trans-fused oxetanols.Experiments bearing on the selectivity of this process as well as the mechanistic hypothesis are also described.