169124-54-3

Basic information

• Product Name: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone
• Synonyms: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone
• CAS NO: 169124-54-3
• Molecular Weight: 268.472
• Mol File: 169124-54-3.mol
• Article Data: 3

Chemical Properties

• CAS DataBase Reference: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone(CAS DataBase Reference)
• NIST Chemistry Reference: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone(169124-54-3)
• EPA Substance Registry System: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone(169124-54-3)

Safety Data

• Hazardous Substances Data: 169124-54-3(Hazardous Substances Data)

Upstream product

• 169219-60-7 Acetic acid (1S,4R)-4-hydroxy-3,5,5-trimethyl-cyclohex-2-enyl ester 
• 169272-96-2 (1R,4S)-2,6,6-trimethyl-2-cyclohexen-1,4-diol 
• 141037-63-0 (+/-)-trans-2,6,6-trimethyl-2-cyclohexen-1,4-diol 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 1125-21-9 2,6,6-trimethyl-2-cyclohexene-1,4-dione 
• 64809-50-3 (4S)-4-hydroxy-2,6,6-trimethyl-cyclohex-2-en-one 
• 169124-53-2 (1R,4S)-4-tertbutyldimethylsilyl-2,6,6-trimethyl-2-cyclohexen-1-ol 

Downstream Products

• 64809-50-3 (4S)-4-hydroxy-2,6,6-trimethyl-cyclohex-2-en-one 
• 219136-33-1 (1S,4S)-1-{(R)-2-[(1S,2S,6S)-6-tert-Butoxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-4-(tert-butyl-dimethyl-silanyloxy)-2,6,6-trimethyl-cyclohex-2-enol 
• 872315-13-4 (1S,4S)-1-{(S)-2-[(1S,2S,6S)-6-tert-Butoxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-4-(tert-butyl-dimethyl-silanyloxy)-2,6,6-trimethyl-cyclohex-2-enol 
• 872315-14-5 (1R,4S)-1-{(S)-2-[(1S,2S,6S)-6-tert-Butoxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-4-(tert-butyl-dimethyl-silanyloxy)-2,6,6-trimethyl-cyclohex-2-enol 
• 872315-25-8 (1S,4S)-4-(tert-Butyl-dimethyl-silanyloxy)-1-{(R)-2-[(1S,2S)-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-2,6,6-trimethyl-cyclohex-2-enol 
• 872315-28-1 (1S,4S)-4-(tert-Butyl-dimethyl-silanyloxy)-1-{(S)-2-[(1S,2S)-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-2,6,6-trimethyl-cyclohex-2-enol 
• 872315-29-2 (1R,4S)-4-(tert-Butyl-dimethyl-silanyloxy)-1-{(S)-2-[(1S,2S)-2-(tert-butyl-dimethyl-silanyloxymethyl)-1-methyl-3-methylene-cyclohexyl]-1-methoxymethoxy-ethyl}-2,6,6-trimethyl-cyclohex-2-enol 

Relevant articles and documents

Precursors to damascenone: Synthesis and hydrolysis of isomeric 3,9-dihydroxymegastigma-4,6,7-trienes

A series of four isomeric 3,9-dihydroxymegastigma-4,6,7-trienes, 8, has been prepared. The (3S,6R,9S) isomer of 8 proved to be identical to an isomer of this compound tentatively identified as an intermediate in the formation of damascenone from an allene triol. Each of the four isomers, when hydrolyzed independently of each other at pH 3.0 and 25°C, produced product mixtures in which the major product was damascenone (1). Contrary to expectation, 3-hydroxydamascone (5) was not observed in any of the hydrolyses. Consequently, the mechanism of formation of damascenone proposed earlier requires modification. In each hydrolysis, the product mixtures showed the presence of a second isomer of 8, produced by epimerization during hydrolysis. Chiral analysis on a Cyclosil B column revealed that this epimerization was occurring at C3 in each of the hydrolyses.

Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives

Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenone, trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (±)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6,6-trimethyl-2-cyclohexen-1-ol (81%ee) and (1S,4R)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92%ee). Hydrolysis of the former monoacetate and recrystallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S,4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 4R)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and (R)-silyloxy enones over Raney nickel afforded the corresponding dihydro derivatives.