61898-90-6

Upstream product

• 109261-42-9 2-((R)-α-deuterio-benzyl)-acetoacetic acid ethyl ester 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 1896-62-4 (E)-benzalacetone 
• 3101-96-0 1-deuterio-1-phenylethanol 
• 74705-64-9 4-phenyl<2-(2)H>but-3-en-2-ol 
• 591-50-4 iodobenzene 
• 98299-96-8 C₄H₆⁽²⁾H₂O 
• 69535-61-1 (R)-α-deuteriobenzyl tosylate 
• 4181-90-2 (R)-(α-2H)benzyl alcohol 

Downstream Products

• 2515-46-0 3-methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole 
• 29453-61-0 (R)-1-deuterio-1-phenyl-butane 

Relevant academic research and scientific papers

Highly efficient redox isomerization of allylic alcohols and transfer hydrogenation of ketones and aldehydes catalyzed by ruthenium complexes

A dicationic dichloro-bipyridine-ruthenium complex shows very high catalytic activity in redox isomerization of allylic alcohols but a relatively low one in transfer hydrogenation of ketones; surprisingly, the analogous dimethyl-bipyridine-ruthenium complex shows reverse catalytic activities in the two reactions.

Secondary Phosphine Oxides as Multitalented Preligands En Route to the Chemoselective Palladium-Catalyzed Oxidation of Alcohols

Secondary phosphine oxides O=PHR2 (SPOs) were identified as multitalented preligands for the chemoselective Pd-catalyzed oxidation of alcohols by a hydrogen-abstracting methodology. SPOs were found to promote the hydrogen-abstraction step as well as hydrogen transfer to a Michael acceptor by generating a putative active H?Pd species. The catalytic system operates under neutral conditions and was proven to be compatible with various electrophilic and nucleophilic functionalities within the substrates as well as water- and air-sensitive functional groups.

General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand

Remarkably simple IrIIIcatalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.

Highly Chemoselective Palladium-Catalyzed Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds with Silicon Hydrides and Zinc Chloride Cocatalyst

A three-component system comparised of a soluble palladium catalyst, hydridosilane, and zinc chloride is capable of efficient conjugate reduction of α,β-unsaturated ketones and aldehydes.The optimal set of condition includes diphenylsilane as the most effective hydride donor, any soluble palladium complex in either the 0 or II oxidation state, when it is stabilized by phosphine ligands, and ZnCl2 as the best Lewis acid cocatalyst.The reaction is very general with respect to a broad range of unsaturated ketones and aldehydes, and it is highly selective for these Michael acceptors, as reduction of α,β-unsaturated carboxylic acid derivatives is very sluggish under these conditions.When dideuteriodiphenylsilane is used to reduce unsaturated ketones, deuterium is stereoselectively introduced at the less-hindered face of the substrate and regioselectively at the β-position.Conversely, when reductions are carried out in the presence of traces of D2O, deuterium incorporation occurs at the α-position.On the basis of deuterium-incorporation experiments and 1H NMR studies, a catalytic cycle is postulated in which the first step involves reversible coordination of the palladium complex to the electron-deficient olefin and oxidative addition of silicon hydride to form a hydropalladium olefin complex.Migratory insertion of hydride into the coordinated olefin produces an intermediate palladium enolate which, via reductive elimination, collapses back to the Pd(0) complex and a silyl enol ether, which is then hydrolyzed to the saturated ketone.In addition to catalyzing that hydrolysis, ZnCl2 facilitates the hydrosilation process.

ZINC CHLORIDE-MEDIATED CONJUGATE REDUCTION WITH SILICON HYDRIDES AND PALLADIUM(0) CATALYST

The chemistry of diphenylsilane/Pd(0), a system previously known to reduce only allylic heterosubstituents, has been radically altered by addition of catalytic amounts of zinc chloride, enabling efficient conjugate reduction of α,β-unsaturated ketones and aldehydes.

PHENYLATION D'ALCOOLS ALLYLIQUES ACYCLIQUES IIa.REGIOSELECTIVITE DU TRANSFERT D'HYDROGENE

PdCl2, HNaCO3-catalysed phenylation of deuterium-labelled allylic butenols, a Heck type reaction, proceeds by a highly regioselective 1,2-hydrogen shift via a Wacker type intermediate.No decomplexed enol was formed during this reaction.