71268-56-9

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 1193-47-1 2,2-dimethyl-cyclohexanone 
• 71268-63-8 2-methyl-2-(phenylthiomethyl)-1-cyclohexanone 
• 19980-35-9 1-trimethylsilyloxy-2-methyl-1-cyclohexene 

Downstream Products

• 71268-57-0 2,2-dimethyl-6-phenylthiomethylcyclohexanone 
• 344305-43-7 6-(Hydroxy-phenyl-methyl)-2,2-dimethyl-cyclohexanone 
• 71268-58-1 2,2-dimethyl-6-methylenecyclohexan-1-one 

Relevant academic research and scientific papers

2-TOSYLOXYMETHYLCYCLANONES: RING SIZE DEPENDENCE OF FRAGMENTATION VERSUS INTRAMOLECULAR ALKYLATION

The results reported seem to indicate, that in the presence of a nucleophilic base intramolecular alkylation is the normal reaction mode of tosyloxymethylcyclanones of type 14 and that the fragmentation reaction of five-membered compounds is the exception, probably because of the high steric energy of the alkylation transition states, e.g. of type E.

α-ALKYLATION AND α-ALKYLIDENATION OF CARBONYL COMPOUNDS BY O-SILYLATED ENOLATE PHENYLTHIOALKYLATION

For many reactions next to a carbonyl group, the use of O-silylated enolate chemistry offers improvements in yield and selectivity over the corresponding reactions of Group I metal enolates.In the case of α-alkylation of carbonyl compounds, Lewis acid (TiCl4 or ZnBr2) promoted phenylthioalkylation of O-silylated enolates 3 by α-chlorosulphides 4 (R3=H, Me, Prn, Pri, Bui, and Me3Si), followed by reductive sulphur removal by Raney nickel, 5->6, is found to be a reliable method for this synthetically important C-C bond forming step.An alternative sulphur elimination pathway via the sulphoxide, 5->7, allows the regio- and stereocontrolled α-alkylidenation of carbonyl compounds.The phenylthioalkylation reaction is applicable to ketones, aldehydes, esters, and lactones.