40638-92-4

Upstream product

• 101-97-3 Ethyl 2-phenylethanoate 
• 103-82-2 phenylacetic acid 
• 101-41-7 benzeneacetic acid methyl ester 
• 536-74-3 phenylacetylene 
• 122-78-1 phenylacetaldehyde 

Downstream Products

• 36809-05-9 2-phenylethyl-1,1-d2-p-toluenesulfonate 
• 29372-33-6 α,α-dideuterated hydrocinnamaldehyde 
• 17428-98-7 2-[D₂]-3-phenylpropan-1-ol 
• 54845-21-5 (3-bromopropyl-2,2-d₂)benzene 
• 1390620-64-0 1,1,3,3-tetradeutero-2,3-diphenylpropan-1-ol 
• 66255-92-3 rac-(β,β-²H₂)styrene oxide 
• 66997-34-0 2-phenylethyldimethylamine-1,1-d2 oxide 
• 66997-32-8 2-phenylethyldimethylamine-1,1-d2 
• 19136-97-1 α-dideuterated 3-phenyl propionic acid 
• 60468-24-8 (2-deuterio-2-propenyl)benzene 
• 40638-88-8 1-chloro-2-phenyl-1,1-d2 ethane 
• 33090-16-3 1-iodo-2-phenylethane-α,α-d2 

Relevant academic research and scientific papers

Aerobic Oxidative Dehydrogenation of Ketones to 1,4-Enediones

An efficient and unprecedented strategy for the synthesis of 1,4-enediones from saturated ketones has been developed via palladium-catalyzed oxidative dehydrogenation. The protocol employs molecular oxygen as the sole oxidant and represents an atom- and step-economic process. The approach showed broad substrate scope, good functional group tolerance, and complete E-stereoselectivity. The reaction mechanism has been investigated through deuterium-labeling experiments and intermediate experiments.

Nickel-Catalyzed Electrochemical Reductive Relay Cross-Coupling of Alkyl Halides to Aryl Halides

A highly regioselective Ni-catalyzed electrochemical reductive relay cross-coupling between an aryl halide and an alkyl halide has been developed in an undivided cell. Various functional groups are tolerated under these mild reaction conditions, which pro

A Method for Bischler-Napieralski-Type Synthesis of 3,4-Dihydroisoquinolines

A new method for the Bischler-Napieralski-type synthesis of 3,4-dihydroisoquinolines was developed by a Tf2O-promoted tandem annulation from phenylethanols and nitriles. Its success was mainly due to the fact that a phenonium ion was formed in the process and practically functioned as a stable and reactive primary phenylethyl carbocation.

Vicinal Diboration of Alkyl Bromides via Tandem Catalysis

Vicinal diboration of alkyl bromides via tandem catalysis is reported. The reported reaction exhibits a broad substrate scope, good functional group compatibility, and regioselectivity. Moreover, it shows good practicality due to the easy accessibility of alkyl bromides in combination with diverse transformations of diboronates. Mechanism study indicates that terminal alkenes are generated selectively through nickel-catalyzed dehydrohalogenation of alkyl bromides followed by base/MeOH promoted diboration process to provide 1,2-diboration products.

Alkene migration to the end-terminal carbon bearing a phenyl group over a chiral siloxy carbon center in Heck reaction

Abstract The Heck reaction of aryl bromide with a terminal alkene substrate having a chiral center at the allylic position and a phenyl substituent at another terminal carbon is reported. An alkene migration to the phenyl-substituted end carbon is observed, along with the typical Heck reaction. This zipper-type migration occurs through multiple internal carbon bonds, and the stereochemistry of the internal chiral center is completely retained during this process.

A highly active and air-stable ruthenium complex for the ambient temperature anti-markovnikov reductive hydration of terminal alkynes

The conversion of terminal alkynes to functionalized products by the direct addition of heteroatom-based nucleophiles is an important aim in catalysis. We report the design, synthesis, and mechanistic studies of the half-sandwich ruthenium complex 12, which is a highly active catalyst for the anti-Markovnikov reductive hydration of alkynes. The key design element of 12 involves a tridentate nitrogen-based ligand that contains a hemilabile 3-(dimethylamino) propyl substituent. Under neutral conditions, the dimethylamino substituent coordinates to the ruthenium center to generate an air-stable, 18-electron, κ3-complex. Mechanistic studies show that the dimethylamino substituent is partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate aldehyde, operate concurrently in reactions mediated by 12. A wide array of terminal alkynes are efficiently processed to linear alcohols using as little as 2 mol % of 12 at ambient temperature, and the complex 12 is stable for at least two weeks under air. The studies outlined herein establish 12 as the most active and practical catalyst for anti-Markovnikov reductive hydration discovered to date, define the structural parameters of 12 underlying its activity and stability, and delineate design strategies for synthesis of other multifunctional catalysts.

Diagnostic fragmentations of adducts formed between carbanions and carbon disulfide in the gas phase. A joint experimental and theoretical study

Selected carbanions react with carbon disulfide in a modified LCQ ion trap mass spectrometer to form adducts, which when collisionally activated, decompose by processes which in some cases identify the structures of the original carbanions. For example (i) C6H5- + CS 2→ C6H5CS2-→ C6H5S- + CS, occurs through a 3-membered ring ipso transition state, and (ii) the reaction between C6H 5CH2- and CS2 gives an adduct which loses H2S, whereas the adduct(s) formed between o-CH 3C6H5- and CS2 loses H2S and CS. Finally, it is shown that decarboxylation of C 6H5CH2CH2CO2- produces the β-phenylethyl anion (PhCH2CH2 -), and that this thermalized anion reacts with CS2 to form C6H5CH2CH2CS2 - which when energized fragments specifically by the process C 6H5CH2CH2CS2 -→ C6H5CH2-CHC(S)SH → [(C6H5CH2CHCS) -SH] → C6H5CH2CCS- + H2S. Experimental findings of processes (ii) and (iii) were aided by deuterium labelling studies, and all reaction profiles were studied by theoretical calculations at the UCCSD(T)/6-31+G(d,p)//B3LYP/6-31+G(d,p) level of theory unless indicated to the contrary.

The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study

The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement with the experimental values for both substrates, but only when migratory extrusion of CO was selected as the rate-determining step.

Incorporation of deuterium-labelled analogs of isopentenyl diphosphate for the elucidation of the stereochemistry of rubber biosynthesis

A series of six deuterium-labelled analogs of isopententyl diphosphate (IPP) was prepared to investigate the detailed stereochemical course of addition of C5 units during rubber biosynthesis in Hevea brasiliensis and Parthenium argentatum. These analogs were incorporated into the cis-polyisoprene chain by rubber transferase in rubber particles, and the stereochemistry was determined by 2H-NMR analysis of the polymer or of levulinic acid derivatives obtained from its ozonolytic degradation. Results indicate that rubber chain elongation occurs with loss of the pro-S hydrogen of IPP, addition of the allylic diphosphate to the si face of IPP and inversion of stereochemistry at the carbon bearing the diphosphate. The Royal Society of Chemistry.

Efficient syntheses of four stable-isotope labeled (1R)-menthyl (1S,2S)-(+)-2-phenylcyclopropanecarboxylates

Many carbenoid cyclopropanation reactions promoted by chiral catalysts give product mixtures reflecting impressive diastereo- and enantioselectivities. Few provide a single chiral product efficiently. This limitation has been overcome in cyclopropanations of styrene and isotopically labeled styrenes with α-diazoacetates. Convenient syntheses on a 20 g scale of each of four chiral isotopically labeled (1R)-menthyl (1S,2S)-2- phenylcyclopropanecarboxylates (the 1-d-3-13C, 1,(3S)-d2, 1,2,(3S)-d3, and 1,3,3-d3 isotopomers) of better than 99% ee have been realized. The Royal Society of Chemistry 2006.