77192-24-6

Upstream product

• 2021-28-5 ethyl dihydrocinnamate 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 1822-00-0 trimethylsilylmethyllithium 
• 645-45-4 hydrocinnamic acid chloride 
• 2550-26-7 4-Phenyl-2-butanone 
• 75-77-4 chloro-trimethyl-silane 
• 6683-51-8 2-methyl-4-phenyl-1-butene 

Downstream Products

• 1266145-46-3 C₁₅H₁₈O 
• 1266145-52-1 C₁₇H₂₂O 
• 1380233-02-2 (5,5,5-trifluoro-3-methylenepentyl)benzene 
• 1448863-22-6 (1R)-3-methylene-5-phenyl-1-m-tolylpentanol 
• 1448863-21-5 (1R)-3-methylene-1-(naphth-2-yl)-5-phenylpentanol 
• 192195-29-2 ethyl (2-methylene-4-phenylbutoxy)acetate 
• 192195-17-8 1-diazo-3-(2-methylene-4-phenylbutoxy)-2-propanone 
• 75074-59-8 4-phenyl-2-(hydroxymethyl)but-1-ene 
• 774199-12-1 4-phenyl-2-trimethylsilanylmethyl-butane-1,2-diol 

Relevant academic research and scientific papers

Asymmetric counteranion-directed catalytic hosomi-sakurai reaction

Counteranion control enables the enantioselective, organo Lewis acid catalyzed Hosomi-Sakurai reaction of (hetero)aromatic aldehydes and allylsilanes using an easily handled disulfonimide precatalyst (see scheme). The key to the success of this system is to turn the usually undesired silylium ion catalysis into the desired catalytic regime and pair the cation with an enantiopure disulfonimide anion, thereby applying the concept of asymmetric counteranion-directed catalysis.

Dianions of 4-phenylbut-1-ene. Evidence for complex-induced proximity effects in the double metallation of hydrocarbons

Metallation of 2-methyl-4-phenylbut-1-ene 1 resulted in the formation of a dianion linearly conjugated with the phenyl ring rather than the cross-conjugated dianion often seen in these systems.Examination of the reaction mixtures at varying periods of time revealed that the initial deprotonation was not at the benzylic carbon.Complexation of n-butyllithium-tetramethylethylenediamine (TMEDA) with the aromatic ring of 1 (a complex-induced proximity effect, CIPE) enhances tha rate of metallation at the carbon β to the aromatic ring and α to the double bond of 1, as demonstrated in competitive metallations of 1 with ethylbenzene and of 1 with hexa-1,5-diene.This is the first report of a complex-induced proximity effect in the double metallation of a hydrocarbon in which complexation occurred with the neutral hydrocarbon.

AN EFFICIENT METHOD FOR CONVERSION OF CARBOXYLIC ACID DERIVATIVES TO ALLYLSILANES

Treatment of acid halides with trimethylsilylmethyl cerium dichloride affords bis β-silylethyl tertiary alcohols which efficiently undergo a trimethylchlorosilane-promoted Peterson reaction to generate allylsilanes in high overall yield.

Controlling the Outcome of a Carbocation-Initiated Cyclisation

The allylsilane, 6,6-dimethoxy-2-(trimethylsilylmethyl)hex-1-ene (2) gives 3-methylenecyclohexyl methyl ether (7) on treatment with tin (IV) chloride, whereas cyclisation of the corresponding compound without the silyl group (1) was known to give five products (5)-(6).The synthesis of the allylsilane (2) is described.