26205-40-3

Upstream product

• 917-64-6 methyl magnesium iodide 
• 25438-37-3 phenyl(trimethylsiloxy)acetonitrile 
• 532-28-5 (RS)-mandelonitrile 
• 33861-17-5 phenyl trimethylsilyl selenide 
• 579-07-7 1-Phenylpropane-1,2-dione 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 75-77-4 chloro-trimethyl-silane 
• 90-63-1 (RS)-1-hydroxy-1-phenylpropan-2-one 
• 2114-00-3 2-bromo-1-phenyl-1-propanone 
• 43108-63-0 1-phenyl-2-trimethylsiloxy-1-propene 

Relevant academic research and scientific papers

A new zincate-mediated rearrangement reaction of 2-(1-hydroxyalkyl)-1- alkylcyclopropanol

A novel rearrangement of 2-(1-hydroxyalkyl)-1-alkylcyclopropanol has been found. It proceeds in the presence of a catalytic amount of organozinc ate complex to give vic-diols. The rearrangement can be applied to various types of 2-(1-hydroxyalkyl)-1-alkyl-cyclopropanol, which can be easily prepared from the corresponding α,β-ep-oxyketones and bis(iodozincio)methane. When bicyclo[13.1.0]-pentadecane-1, 15-diol was treated with the organozinc ate complex, the corresponding 14-membered cyclic vic-diol was obtained. Thus, this rearrangement is also useful for changing the ring size of cyclic substrates.

Reaction of carbonyl compounds with trialkylsilyl phenylselenide and tributylstannyl hydride under radical conditions

A novel method for the hydrosilylation of carbonyl compounds has been developed. When carbonyl compounds were allowed to react with trimethylsilyl phenylselenide and tributylstannyl hydride in the presence of a catalytic amount of AIBN as the radical initiator, hydrosilylation of the carbonyl compounds efficiently proceeded to give the corresponding silyl ethers in moderate to good yields. In the absence of carbonyl compounds, the triethylsilyl hydride was obtained by the reaction of PhSeSiEt3 with Bu3SnH. Although the tributylgermyl phenylselenide instead of PhSeSiMe3 was treated with tributylstannyl hydride in the presence of a benzaldehyde under radical conditions, hydrogermylated product was not obtained and tributylgermyl hydride was mainly formed.

Hydrosilylation of carbonyl compounds using a PhSeSiMe3/Bu3SnH/AIBN system

(equation presented) When carbonyl compounds were allowed to react with phenyl trimethylsilyl selenide and tributylstannyl hydride in the presence of a catalytic amount of AIBN as a radical initiator, the hydrosilylation of the carbonyl compounds efficiently proceeded to give the corresponding silyl ethers in moderate to good yields.

Palladium- or Platinum-Catalyzed Novel Double Silylation of α-Diketones or a Benzoylformate with Hexamethyldisilane Affording 1,2-Bis(siloxy)ethenes or a Double Silylated Tartrate Derivative

α-Diketones (benzil, methyl phenyl diketone, acenaphthenequinone, camphorquinone) reacted with hexamethyldisilane in the presence of a Pd or Pt catalyst (PdCl2(PMe3)2, Pt2(dba)3-P(OCH2)3CEt, etc.) to give the corresponding 1,2-bis(trimethylsiloxy)ethenes in excellent to moderate yields, while methyl benzoylformate provided dimethyl 2,3-diphenyl-2,3-bis(O-trimethylsilyl)tartrate.

Applications of Optically Active Aryl Cyanohydrins in the Synthesis of α-Hydroxy Aldehydes, α-Hydroxy Ketones and β-Hydroxy Amines

Cyanohydrins, prepared in high optical purity from aryl aldehydes, have been converted into α-hydroxy aldehydes, α-hydroxy ketones and β-hydroxy amines without any racemization and frequently with good stereoselectivity for the erythro-diastereoisomer (>90percent) at the newly introduced stereogenic centre.