68566-80-3

Upstream product

• 41203-27-4 1-chloro-1-deuterio-1-phenylethane 
• 10606-76-5 (R)-2-phenylethyl 4-methylbenzenesulfonate 
• 1459-15-0 (R)-1-chloro-1-phenylethane 
• 672-65-1 (1-chloroethyl)benzene 
• 1459-14-9 (R)-(1-bromoethyl)benzene 
• 16355-00-3 (R)-1-phenyl-1,2-ethanediol 
• 60208-56-2 (R)-(+)-2-d₁-phenylethanol 
• 611-71-2 (R)-Mandelic Acid 
• 20698-91-3 (R)-methyl mandelate 
• 286967-46-2 2-methoxy-2-methyl-4-phenyl-1,3-dioxolane 
• 33942-00-6 (S)-(-)-2-chloro-2-phenethylacetic acid 
• 71886-64-1 (S)-α-Deuterio-α-phenylethanol 
• 3756-40-9 (S)-(-)-α-phenethyl bromide 
• 585-71-7 (1-bromoethyl)benzne 

Downstream Products

• 3101-96-0 1-deuterio-1-phenylethanol 
• 98-85-1 1-Phenylethanol 
• 1445-91-6 (S)-1-phenylethanol 
• 1517-69-7 (R)-1-phenylethanol 
• 71886-64-1 (S)-α-Deuterio-α-phenylethanol 
• 71886-65-2 1-deuterio-(R)-(+)-1-phenylethanol 

Relevant academic research and scientific papers

Optically Active 1-Deuterio-1-phenylethane – Preparation and Proof of Enantiopurity

Enantiopure (S)-(1-2H)ethylbenzene was prepared in two steps from optically active (S)-1-phenylethanol via (R)-(1-chloroethyl)benzene (two inversions of configuration). Since the value for the specific rotation [α] is very low for the enantiomers of (1-2H)ethylbenzene, the enantiopurity of the synthetic product could not be determined with certainty by polarimetry. Therefore, bis-sulfonamides were prepared by twofold chlorosulfonation (para and ortho) of (S)-(1-2H)ethylbenzene and subsequent amidation with (R)- and (S)-α-phenethylamine. For both diastereoisomers, the (R,R,S)- and the (S,S,S)-sulfonamides, 92 % de was determined by 1H NMR spectroscopy. Therefore, it could be concluded, that (S)-(1-2H)ethylbenzene had been obtained with 92 % ee.

High-throughput method for determining the enantioselectivity of enzyme-catalyzed hydroxylations based on mass spectrometry

(Chemical equation presented) Up to speed: An accurate, sensitive, high-throughput, and simple method for measuring the product ee value of enzyme-catalyzed hydroxylations (see scheme) is based on the use of enantiopure or enantioenriched deuterated substrates and mass spectrometric detection.

Kinetics and mechanism of the reaction of benzyl halides with zinc in dimethylformamide

The reaction of metal zinc with various benzyl halides in dimethylformamide has been studied. The low-temperature ESR-spectroscopy is used to show that reaction of zinc with benzyl bromide and benzyl iodide occurs to form benzyl radicals. Benzyl chloride reacts with zinc at 77 K to form benzyl radicals and ion-radical pairs RX- - Zn+. Nevertheless these pairs disappear at temperatures higher than 110 K. The investigation of the reaction stereochemistry and the use of a radical trap provide evidence in favor of a radical mechanism. The optical activity has been proved in the course of the formation of organozinc halide from (+)-R-1-halogen-1-phenylethane at low temperature. The kinetic features of the reaction have been studied. Benzyl iodide reacts with zinc at transport-controlled rate. The reaction of zinc with benzyl chloride and benzyl bromide in DMF occurs according to Langmuir-Hinshelwood scheme, the adsorption of reagents taking place on similar active centers of metal. The kinetic and thermodynamic parameters of the reaction have been clarified. The comparison of kinetic parameters with those reported in literature evidences that the limiting step of reaction is halogen atom transfer (inner sphere electron transfer). Copyright

Reaction of magnesium with benzyl halides in an optically active solvent

Grignard reagent formation from benzyl halides with an asymmetric centre in the presence of an optically active solvent proceeds on the magnesium surface within a solvent cage by one-electron transfer mechanism.Keywords: Magnesium; Optical activity

Optical activity retention in the reaction of magnesium with (+)-R-1-chloro-1-phenylethane

Optical activity retention has been proved in the course of the formation of Grignard reagent from optically active (+)-R-1-chloro-1-phenylethane.Key words: Magnesium; Optical activity

Side Chain Hydroxylation of Aromatic Hydrocarbons by Fungi. Part 2. Isotope Effects and Mechanism

The benzylic hydroxylation of ethylbenzene, p-diethylbenzene, tetralin, indane, and toluene by the fungi Mortierella isabellina, Cunninghamella echinulata, and Helminthosporium species has been investigated by the use of deuterium-labelled substrates.An i

Stereochemical Dynamics of Aliphatic Hydroxylation by Cytochrome P-450

Previous studies on the stereochemistry of hydroxylation by cytochrome P-450 enzymes have been contradictory and confusing.Therefore, the hydroxylation of four isotopically substituted phenylethane substrates has been examined with a single isozyme of rabbit liver microsomal cytochrome P-450.In each case the corresponding 1-phenylethanol was essentially the only product.With ordinary phenylethane, the product was 48percent R-1-phenylethanol and 52percent the S isomer.With (R)-phenylethane-1-d, the product was 42percent R alcohol, while with (S)-phenylethane-1-d the product was 70percent R alcohol.When the substrate was phenylethane-1,1-d2, 50percent R alcohol was produced.The alcohols from the single-deuterium-substituted substrates were highly enriched in deuterium, indicating the operation of a large deuterium isotope effect on hydrogen removal.Most importantly, 23-40percent of the hydroxylation events resulted in alcohol with configuration opposite to that of the original hydrocarbon substrate.These "crossover" events require the intermediacy of a discrete tricoordinate carbon intermediate.These data unambiguously demonstrate that hydroxylation stereospecificity must be enforced by the surrounding protein tertiary structure and is not an inherent feature of the cytochrome P-450 reaction mechanism.

FUNGAL HYDROXYLATION OF ETHYL BENZENE AND DERIVATIVES

The fungus Mortierella isabellina converts ethyl benzene and a number of para-substituted derivatives to the corresponding optically active 1-phenylethanols with enantiomeric excesses between 5 and 40percent.Hydrogen removal from the substrate preceeds product formation and is stereochemically independent of it.

Occurrence of Electron Transfer in the Reduction of Organic Halides by LiAlH4 and AlH3

A variety of methods have been utilized to detect the occurrence of a single electron transfer pathway in the reduction of alkyl halides by LiAlH4 and AlH3, i.e., (1) product studies of reduction of cyclizable alkyl halides containing the 5-hexenyl group, (2) trapping of intermediate radicals by dicyclohexylphosphine and other trapping agents, (3) direct EPR observation of the trityl radical in the reduction of trityl bromide, and (4) stereochemical studies of the reduction of secondary halides by lithium aluminum deuteride.The extent of electron transfer was found to be a function of the solvent, the substrate, the leaving group, and the hydride reagent.For alkyl iodides, and to a lesser extent bromides, electron transfer was found to be the major reaction pathway; however, no evidence for electron transfer was found for the corresponding chlorides or tosylates.Reduction of (+)-2-octyl iodide by LiAlD4 was found to be much less stereospecific than the corresponding reduction of bromide, chloride, or tosylate, indicating intermediate radical formation in the reduction of the secondary iodide.