1992-50-3

Upstream product

• 104-53-0 3-phenyl-propionaldehyde 
• 925-90-6 ethylmagnesium bromide 
• 3152-68-9 (1E)-1-phenylpent-1-en-3-one 
• 20795-51-1 1-phenylpentan-3-one 
• 60012-52-4 Phenylsulfonyl-1-phenyl-1-pentanol-3 
• 1992-57-0 1-Anilino-1-phenyl-pentanol-⁽³⁾ 
• 3277-89-2 phenethylmagnesium bromide 
• 123-38-6 propionaldehyde 
• 103-63-9 1-phenyl-2-bromoethane 
• 557-20-0 diethylzinc 
• 10467-10-4 ethylmagnesium iodide 
• 2021-28-5 ethyl dihydrocinnamate 
• 2386-64-3 ethylmagnesium chloride 
• 4436-24-2 1,2-epoxy-3-phenylpropane 

Downstream Products

• 1126479-77-3 2-ethyl-4-phenylbutanenitrile 
• 4830-96-0 (3-chloropentyl)benzene 
• 188432-47-5 Dithiocarbonic acid O-(1-ethyl-3-phenyl-propyl) ester S-methyl ester 
• 51157-53-0 3--1-phenyl-pentan 
• 20795-51-1 1-phenylpentan-3-one 

Relevant academic research and scientific papers

Tandem Oxidative Derivatization of Nitrene Insertion Products for the Highly Diastereoselective Synthesis of 1,3-aminoalcohols

Transition-metal-catalyzed nitrene insertion into tertiary C?H bonds located at stereogenic carbons often results in mixtures of diastereomeric products, especially if the reaction proceeds through a concerted pathway. In this communication, we report a s

Umpolung Strategy for Arene C?H Etherification Leading to Functionalized Chromanes Enabled by I(III) N-Ligated Hypervalent Iodine Reagents

The direct formation of aryl C?O bonds via the intramolecular dehydrogenative coupling of a C?H bond and a pendant alcohol represents a powerful synthetic transformation. Herein, we report a method for intramolecular arene C?H etherification via an umpoled alcohol cyclization mediated by an I(III) N-HVI reagent. This approach provides access to functionalized chromane scaffolds from primary, secondary and tertiary alcohols via a cascade cyclization-iodonium salt formation, the latter providing a versatile functional handle for downstream derivatization. Computational studies support initial formation of an umpoled O-intermediate via I(III) ligand exchange, followed by competitive direct and spirocyclization/1,2-shift pathways. (Figure presented.).

An Intramolecular Iodine-Catalyzed C(sp3)?H Oxidation as a Versatile Tool for the Synthesis of Tetrahydrofurans

The formation of ubiquitous occurring tetrahydrofuran patterns has been extensively investigated in the 1960s as it was one of the first examples of a non-directed remote C?H activation. These approaches suffer from the use of toxic transition metals in overstoichiometric amounts. An attractive metal-free solution for transforming carbon-hydrogen bonds into carbon-oxygen bonds lies in applying economically and ecologically favorable iodine reagents. The presented method involves an intertwined catalytic cycle of a radical chain reaction and an iodine(I/III) redox couple by selectively activating a remote C(sp3)?H bond under visible-light irradiation. The reaction proceeds under mild reaction conditions, is operationally simple and tolerates many functional groups giving fast and easy access to different substituted tetrahydrofurans.

Sulfonium ion-promoted traceless Schmidt reaction of alkyl azides

Schmidt reaction by sulfonium ions is described. General primary, secondary, and tertiary alkyl azides were converted to the corresponding carbonyl or imine compounds without any trace of the activators. This bond scission reaction through 1,2-migration of C-H and C-C bonds was accessible to the one-pot substitution reaction.

2,2′-Bipyridine-α,α′-trifluoromethyl-diol ligand: Synthesis and application in the asymmetric Et2Zn alkylation of aldehydes

A chiral 2,2′-bipyridine ligand (1) bearing α,α′-trifluoromethyl-alcohols at 6,6′-positions was designed in five steps affording either the R,R or S,S enantiomer with excellent stereoselectivities, i.e. 97% de, >99% ee and >99.5% de, >99.5% ee, respectively. The key step for reaching high levels of stereoselectivity was demonstrated to be the resolution of the α-CF3-alcohol using (S)-ibuprofen as the resolving agent. An initial application for the 2,2′-bipyridine-α,α′-CF3-diol ligand was highlighted in the ZnII-catalyzed asymmetric ethylation reaction of aromatic, heteroaromatic, and aliphatic aldehydes. Synergistic electron deficiency and steric hindrance properties of the newly developed ligand afforded the corresponding alcohols in good to excellent yields (up to 99%) and enantioselectivities (up to 95% ee). As observed from single crystal diffraction analysis, the complexation of the 2,2′-bipyridine-α,α′-CF3-diol ligand generates an unusual hexacoordinated ZnII.

Efficient and versatile catalysis for β-alkylation of secondary alcohols through hydrogen auto transfer process with newly designed ruthenium(II) complexes containing ON donor aldazine ligands

A new series of ruthenium(II) carbonyl complexes, [RuCl(CO)(EPh3)2(L1-2)] (1–4) (E?=?P or As; H2L1?=?salicylaldazine, H2L2?=?2-hydroxynaphthaldazine), have been assembled from ruthenium(II) precursors [RuHCl(CO)(EPh3)3] and bidentate ON donor Schiff base ligands (H2L1-2). Both ligands and their new ruthenium(II) complexes have been characterized by elemental analyses, spectroscopic methods (UV, IR, NMR (1H, 13C, 31P) as well as ESI mass spectrometry. The molecular structures of H2L1 and 1 have been confirmed by single crystal X-ray diffraction. Based on the above studies, an octahedral coordination geometry around the metal center has been proposed for 1–4. To investigate the catalytic effectiveness of 1–4, the complexes have been used as catalysts in β-alkylation of secondary alcohols with primary alcohols and synthesis of quinolines. The effect of solvent, time, base, catalyst loading, and substituent of the ligand moiety on the reaction was studied. Notably, 1 was a more efficient catalyst toward alkylation of a wide range of alcohols and quinolines synthesis. The reusability of the catalyst was checked and the results showed up to six catalytic runs without significant loss of activity.

Pure phosphotriesters as versatile ligands in transition metal catalysis: efficient hydrosilylation of ketones and diethylzinc addition to aldehydes

This work aims to highlight the underrated role played by pure phosphotriester (or phosphate) ligands in catalysis, when compared to other phosphorus-containing donors such as phosphane oxides or phosphites. To probe this and to enlarge the very narrow catalytic scope of these Lewis bases, easily accessible mono- and bidentate phosphotriesters were tested as donors in two important transition metal-based catalytic transformations: the zinc-catalyzed hydrosilylation of ketones and the titanium-promoted diethylzinc addition to aldehydes. In both cases, the reactions were successful and the corresponding alcohols were obtained in high yields.

A catalytic system for the activation of diorganozinc reagents

We report a novel catalytic system for the activation of diorganozinc reagents. We assumed that the nucleophilic activation of diethylzinc should be efficiently performed by simple alkali metal salts. Indeed, the combination of sodium salts and 15-crown-5 significantly accelerates the rate of diethylzinc addition to benzaldehyde under mild conditions. The activity of the catalytic system strongly depends on the nature of the anion, decreasing in the order I->Br->Cl->F-. Under the optimized reaction conditions, various aryl, hetero aryl, and aliphatic aldehydes were converted with diethylzinc and the corresponding product was obtained in excellent yields. The first X-ray absorption spectroscopy measurements on such type of reactions provide initial insights that support the proposed catalytic cycle and suggest the formation of a zincate complex.

Synthetic, structural, NMR and catalytic studies of phosphinic amide-phosphoryl chalcogenides (chalcogen = O, S, Se) as mixed-donor bidentate ligands in zinc chemistry

ortho Substituted (diphenylphosphoryl)-, (diphenylphosphorothioyl)- and (diphenylphosphoroselenoyl)-phosphinic amides o-C6H 4(P(X)Ph2)(P(O)NiPr2) (X = O (20a), S (20b), Se (20c)) were synthesized by ortho directed lithiation of N,N-diisopropyl-P,P-diphenylphosphinic amide (Ph2P(O)N iPr2) followed by trapping with Ph2PCl and subsequent oxidation of the o-(diphenylphosphine)phosphinic amide (19) with H2O2, S8 and Se. The reaction of the new mixed-donor bidentate ligands with zinc dichloride afforded the corresponding complexes [ZnCl2(P(X)Ph2)o-C6H 4(P(O)NiPr2)] (21a-c). The new compounds were structurally characterized in solution by nuclear magnetic resonance spectroscopy and in the solid-state by X-ray diffraction analysis of the ligand (20b) and the three complexes (21a-c). The X-ray crystal structure of 20b suggests the existence of a PO→P(S)-C intramolecular nonbonded interaction. The natural bond orbital (NBO) analysis using DFT methods showed that the stabilization effect provided by a nO→σ* P-C orbital interaction was negligible. The molecular structure of the complexes consisted of seven-membered chelates formed by O,X-coordination of the ligands to the zinc cation. The metal is four-coordinated by binding to the two chlorine atoms showing a distorted tetrahedral geometry. Applications in catalysis revealed that hemilabile ligands 20a-c act as significant promoters of the addition of diethylzinc to aldehydes, with 20a showing the highest activity. Chelation of Et2Zn with 20a was evidenced by NMR spectroscopy.

Highly chemoselective reduction of carbonyl groups in the presence of aldehydes

The exquisite ability of diethylaluminum benzenethiolate to efficiently discriminate between aldehydes and other carbonyl functions enables the chemoselective in situ reduction of ketones and methyl esters in the presence of aldehydes. This potent strateg