26205-41-4

Upstream product

• 13735-81-4 1-styrenyloxytrimethylsilane 
• 582-24-1 1-phenyl-2-hydroxyethanone 
• 10416-58-7 N,N-bis(trimethylsilyl)acetamide 
• 70-11-1 α-bromoacetophenone 

Downstream Products

• 4217-66-7 1,2-dihydroxy-2-phenylpropane 
• 16355-00-3 (R)-1-phenyl-1,2-ethanediol 
• 25779-13-9 (S)-1-phenyl-1,2-ethanediol 

Relevant academic research and scientific papers

A convenient synthesis of 2-phenylglycerol

1,3-Dihydroxyacetone dimer is treated with trimethylsilyl chloride and triethylamine in dichloromethane to provide monomeric ketone having both of its alcohols protected as their di-TMS ethers. The latter is added to phenylmagnesium bromide in ether at -78°C. Work-up by treatment with aqueous ammonium chloride followed by 2 N HCl provides 2-phenylglycerol in 70% yield.

Dehomologation of Aldehydes via Oxidative Cleavage of Silyl Enol Ethers with Aqueous Hydrogen Peroxide Catalyzed by Cetylpyridinium Peroxotungstophosphate under Two-Phase Conditions

Dehomologation of aldehydes has been first successfully achieved via oxidative cleavage of silyl enol ethers, derived from aldehydes and trimethylchlorosilane, using aqueous hydrogen peroxide in the presence of a catalytic amount of peroxotungstophophate (PCWP) under phase-transfer conditions. For instance, the oxidation of 1-[(trimethylsilyl)oxy]-1-octene resulting from octanal and Me3SiCl with 35% H2O2 catalyzed by PCWP in dichloromethane at room temperature afforded the one-carbon shorter aldehyde, heptanal, in 79% yield. A variety of silyl enol ethers were also converted into one-carbon shorter aldehydes in good yields. The oxidation under homogeneous conditions using tert-butyl alcohol gave hydrolysis products such as 2-oxooctanol and octanal. It is of interest that [1-(trimethylsilyl)oxy]-1,10-undecadiene involving an enol moiety and a terminal double bond afforded exclusively 9-decenal, in which the enol moiety was selectively oxidized. A plausible reaction path for the oxidative cleavage of silyl enol ethers by the present system has been suggested from the oxidation results of α-[(trimethylsilyl)oxy]styrene.

Reactivity and selectivity in the oxidation of styrene derivatives. V. studies on the oxidation of α-substituted styrenes

The liquid phase oxidation of α-phenyl-1a, α-trimethylsilyloxy 1b, α-cyclopropyl-1c, α-trifluoromethyl-1d styrene, and styrene 1e with oxygen in chlorobenzene and cumene solution in the temperature range 55-125°C was investigated. The product yields were determined gaschromatographically. The epoxide selectivity increases up to 90°C with increasing temperature. The epoxides of 1a and 1c rearrange at higher temperatures, therefore their yield decreases. The relative chain propagation constants (kpC=C) were determined by competitive oxidations of cumene. WILEY-VCH Verlag GmbH, 1999.

Oxygenation of Silyl Enol Ethers and Silyl Ketene Acetals with Molecular Oxygen and Aldehyde Catalyzed by Nickel(II) Complex. A Convenient Method for the Preparation of α-Hydroxy Carbonyl Compounds

In the presence of a catalytic amount of nickel(II) complex, silyl enol ethers and silyl ketene acetals are smoothly oxygenated by the combined use of molecular oxygen and aldehyde to afford α-siloxy carbonyl compounds via possible intermediates, siloxy epoxides.And on treatment of the α-siloxy carbonyl compounds with potassium fluoride α-hydroxy carbonyl compounds are obtained in good to high yields.

Asymmetric Synthesis Using Chirally Modified Borohydrides. Part 3. Enantioselective Reduction of Ketones and Oxime Ethers with Reagents Prepared from Borane and Chiral Amino Alcohols

The asymmetric reduction of aromatic and aliphatic ketones, halogeno ketones, keto esters, and ketone oxime ethers with reagents prepared from borane and chiral amino alcohols has been investigated.When α,α-diphenyl-β-amino alcohols, such as (2S,3R)-(-)-2-amino-3-methyl-1,1-diphenylpentanol (2d), were used as a chiral auxiliary, very high enantioselectivities (ca. 90percent e.e.) were obtained in the reduction of various ketones and oxime ethers.

Induction asymetrique. V. Determination des configurations relatives de γ-amino β-hydroxyesters diastereoisomeres, obtenus par la reaction de Reformatsky

Addition of various Reformatsky reagents (R1-CHZnBr-CO2CH3) to three aromatic α-aminocetones yields mixtures of threo and erythro diastereomeric γ-amino β-hydroxyesters.The relative configurations of the first terms of eac