108612-93-7

Upstream product

• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 38614-36-7 2-methylpropen-1-ylmagnesium bromide 
• 93423-85-9 (2-Methyl-4-oxo-cyclohex-2-enyl)-acetic acid tert-butyl ester 
• 5292-43-3 bromoacetic acid tert-butyl ester 
• 58775-59-0 (4-Ethoxy-2-oxo-cyclohex-3-enyl)-acetic acid tert-butyl ester 
• 75-77-4 chloro-trimethyl-silane 

Downstream Products

• 53-06-5 (+/-)-cortisone 
• 382-45-6 (+/-)-adrenosterone 
• 1882-86-6 (8S,9R,10R,13S,14S)-17-Acetyl-10,13-dimethyl-1,6,7,8,9,10,12,13,14,15-decahydro-2H-cyclopenta[a]phenanthrene-3,11-dione 
• 104621-22-9 [(1S,2R)-2-Methyl-2-(2-methyl-propenyl)-4-oxo-cyclohexyl]-acetaldehyde 
• 122314-70-9 (1S,3S,4R)-4-(2-Hydroxy-ethyl)-3-methyl-3-(2-methyl-propenyl)-cyclohexanol 

Relevant academic research and scientific papers

Stereoselectivity in the Michael Addition Reaction of Dialkylcuprates to the 2-Cyclohexenones with C-4 Ester Substituents

Stereoselectivity in the Michael addition of (Me2C= CH)2CuMgBr and (Me2C=CH)2CuLi to 3-alkyl/H-4-[(tert-butoxycarbonyl)alkyl]-2-cyclohexenone was studied. (Me2C=CH)2CuMgBr showed stereoselectivity in all cases (3-H, Me: anti; 3-n-Bu: syn). This stereoselectivity disappeared in the reaction of (Me2C=CH)2CuLi with 4-[(tert-butoxycarbonyl)methyl]-3-butyl-2-cyclohexenone. However, the stereoselectivity was recovered by elongating the 4-alkyl chain of 2-cyclohexenone to show the same selectivity as that of (Me2C=CH)2CuMgBr.

Total Synthesis of ( +/-)-Cortisone. Double-Hydroxylation Reaction for Corticoid Synthesis

Total syntheses of (+/-)-cortisone and (+/-)-adrenosterone have been achieved in 18 steps with the aid of metal-assisted new synthetic sequences in particular, ene reaction and homoenolate chemistry.A novel double-hydroxylation reaction of enol silyl ethers leading to a single step construction of the dihydroxyacetone side chain in corticoids has been developed and applied to the synthesis of cortisone, cortexolone, and 16α-methylcortexolone.

CHLOROSILANE-ACCELERATED CONJUGATE ADDITION OF CATALYTIC AND STOICHIOMETRIC ORGANOCOPPER REAGENTS

Trialkylsilyl chlorides, particularly in combination with hexamethylphosphoramide or 4-dimethylaminopyridine, dramatically accelerates the conjugate addition of catalytic and stoichiometric organocopper reagents onto enones, enals, and enoates, in which very high degrees of stereo- and chemoselectivities were observed.

Me3SiCl/HMPA ACCELERATED CONJUGATE ADDITION OF CATALYTIC COPPER REAGENT. STEREOSELECTIVE SYNTHESIS OF ENOL SILYL ETHER OF ALDEHYDE

Copper-catalyzed conjugate addition of Grignard reagents in the presence of Me3SiCl and HMPA proceeds in much higher yield than the reaction of conventional organocopper reagents and shows very good regio-, stereo-, and chemoselectivities.