3528-07-2

Upstream product

• 434-45-7 2,2,2-Trifluoroacetophenone 
• 770-09-2 benzyltrimethylsilane 
• 75-77-4 chloro-trimethyl-silane 
• 645-49-8 cis-stilben 
• 107-87-9 2-Pentanone 
• 96-22-0 pentan-3-one 
• 120-92-3 cyclopentanone 
• 108-94-1 cyclohexanone 
• 563-80-4 3-methyl-butan-2-one 
• 58971-25-8 4-methylbenzenesulfonic acid 1-(trimethylsilyl)hydrazide 
• 501-65-5 diphenyl acetylene 

Relevant academic research and scientific papers

Mg-Promoted Regioselective Cross-Coupling of Stilbene Derivatives with Carbonyl Compounds

Treatment of stilbene derivatives with aliphatic carbonyl compounds in the presence of trimethylsilyl chloride (TMSCl) and Mg metal in N,N- dimethylformamide (DMF) at room temperature brought about regioselective cross-coupling to give the corresponding phenethyl alcohols in moderate to good yields. These reactions may be initiated through one-electron transfer from Mg metal to the carbon-carbon double bond of stilbene derivatives to give the corresponding anion radical species, which were subjected to electrophilic attack of aliphatic carbonyl compounds followed by fast second electron transfer generating the corresponding α-benzyl anions.

SET and exciplex pathways in the photochemical reactions between aromatic ketones and benzylsilane and stannane derivatives

The photochemical reaction of α,α,α-trifluoroacetophenone (TFA), benzophenone, and p-cyanoacetophenone with benzyltrimethylsilane in MeCN involves hydrogen transfer from the benzylic position. Desilylation occurs as a minor process only in the case of TFA (but it increases greatly in the presence of MeOH or LiClCO4). The final products result from the statistical recombination of the benzyl and ketyl radicals. Further cases of intramolecular selectivity studied are p-methylbenzyl- and p-methoxybenzyltrimethylsilane (the latter substrate undergoes mainly C-Si bond cleavage in the reaction with TFA) as well as benzyltributylstannane (only destannylation observed with all ketones). Product studies are complemented by the determination of relevant kinetic parameters through steadystate and flash-photolysis experiments. The results are explained in terms of hydrogen transfer proceeding from an exciplex and desilylation from the solvent separated radial ion pair. The latter species predominates when ΔGet -1.