184481-14-9

Upstream product

• 184481-13-8 (3S,3aR,7S,7aS)-7-(tert-Butyl-diphenyl-silanyloxy)-7a-methyl-3-(2-methyl-allyl)-octahydro-inden-4-one 
• 57356-77-1 4-acetoxy-3-methyl-2-cyclohexen-1-one 
• 917-54-4 methyllithium 
• 184653-98-3 (3S,3aS,7S,7aS)-7-(tert-Butyl-diphenyl-silanyloxy)-7a-methyl-3-(2-methyl-allyl)-octahydro-inden-4-one 
• 136611-26-2 (S)-4-<(t-butyldiphenylsilyl)oxy>-3-methyl-2-cyclohexenone 
• 184481-12-7 (3S,4S)-4-(tert-Butyl-diphenyl-silanyloxy)-3-(2-[1,3]dioxan-2-yl-ethyl)-3-methyl-cyclohexanone 
• 184481-09-2 (7S,7aS)-7-(tert-Butyl-diphenyl-silanyloxy)-7a-methyl-1,2,5,6,7,7a-hexahydro-inden-4-one 
• 58479-61-1 tert-butylchlorodiphenylsilane 
• 136658-04-3 (-)-4-acetoxy-3-methyl-2-cyclohexen-1-one 
• 136658-05-4 (S)-4-hydroxy-3-methyl-cyclohex-2-en-1-one 

Relevant academic research and scientific papers

Concise total syntheses of the sesquiterpenoids (-)-homalomenol A and (-)-homalomenol B

The conjugate additions of the organocopper(I) reagents 22 and 27 to the enantiomerically homogeneous bicyclic enone 4 provided, after epimerization (NaOMe, MeOH) of the resultant product mixtures and appropriate chromatographic separations, the bicyclo[4.3.0]nonan-2-ones 24 and 28. Compounds 24 and 28 were readily converted, via two synthetic steps in each case, into the sesquiterpenoids (-)-homalomenols B (2) and A (1), respectively.

Cis-trans isomerization and oxidation of radical cations of stilbene derivatives

Isomerization from cis stilbene derivatives (c-S (S = RCH=CHC6H5: 1, R = C6H5; 2, R = 4-CH3C6H4; 3, R = 4-CH3OC6H4 (= An); 4, R = 2,4-(CH3O)2C6H3; 5, R = 3,4-(CH3O)2C6H3; 6, R = 3,5-(CH3O)2C6H3; 7, AnCH=C(CH3)C6H5; 8, AnCH=CHAn)) to trans isomers (t-S) and oxidation of S with O2 were studied in γ-ray radiolyses of c-S in Ar-saturated 1,2-dichloroethane (DCE) and of S in O2-saturated DCE, respectively. On the basis of product analyses, it is suggested that a smaller barrier to c-t unimolecular isomerization for c-3.+-5.+ and 8.+ than for c-1.+, 2.+, and 6.+ due to the single bond character of the central C=C double bond for c-3.+-5.+ and 8.+ with a p-methoxyl group but not for c-l.+, 2.+, and 6.+ without a p-methoxyl group because of the contribution of a quinoid-type structure induced by charge-spin separation. The isomerization proceeds via chain reaction mechanisms involving c-t unimolecular isomerization and endergonic hole transfer or dimerization and decomposition. The isomerization of c-3.+ to t-3.+ is catalyzed by addition of 1,4-dimethoxybenzene but terminated by triethylamine. The regioselective formation of 3d in oxidation of 3.+ with O2 is explained by spin localization on the β-olefinic carbon in 3.+. The results of product analyses are compared with the rate constants of the unimolecular isomerization and the oxidation for S.+ measured with pulse radiolyses.