Search results for "Protonation"
showing 10 items of 583 documents
Enantioselective Synthesis of Tetrahydroprotoberberines and Bisbenzylisoquinoline Alkaloids from a Deprotonated α-Aminonitrile
2011
Under controlled conditions, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile can be quantitatively deprotonated in the α-position. Its alkylation directly furnishes 3,4-dihydroisoquinolines which can serve as starting materials for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine, (+)-armepavine, and (+)-laudanosine as well as the tetrahydroprotoberberines (-)-corytenchine and (-)-tetrahydropseudoepiberberine using Noyori's asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O-methylthalibrine and (+)-tetramethylmagnolamine were obtained from nonracemic precursors in Ullmann diaryl ether syntheses.
Catalytic Asymmetric Addition of Dimethylzinc to α-Ketoesters, Using Mandelamides as Ligands
2006
[reaction: see text] A strategy based on the control of the electron-donating capabilities of the coordinating groups of the ligand has been applied in the catalytic asymmetric addition of organometallic reagents to ketoesters. Mandelamides having deprotonated alcohol and carboxyamido groups catalyzed the addition of dimethylzinc to alpha-ketoesters with good yields and ee (up to 90%).
Enhanced Acid Dissociation at the Solid/Liquid Interface
2019
In this chapter we review some recent results from first principles molecular dynamics simulations which show how molecular properties, such as proton dissociation, can be influenced upon adsorption at a solid/liquid interface. In particular, we discuss in details the increased acidity of pyruvic acid at the quartz /water interface, which is of relevance for the chemistry of the atmosphere. Our simulations unveil the special role of the microsolvation at interface, as well as the role of the silanols in stabliziing the deprotonated form of the acid. The enhanced acidity at the hydrophilic quartz/water interface is at odd with what typically found at the water/air interface where acidity is …
Enantioselective Synthesis of (−)-Dihydrocodeine and Formal Synthesis of (−)-Thebaine, (−)-Codeine, and (−)-Morphine from a Deprotonated α-Aminonitri…
2014
The α-benzylation of a deprotonated bicyclic α-aminonitrile, followed by Noyori's asymmetric transfer hydrogenation combined with the Grewe cyclization onto a symmetrical A-ring precursor, are the key steps of a short and high-yielding enantioselective synthesis of the morphinan (-)-dihydrocodeine. This compound can be converted to (-)-thebaine in high yield by known transformations, while (-)-codeine and (-)-morphine are available from an advanced intermediate.
Controlled Activation of Substrate Templating in Molecular Self-Assembly by Deprotonation
2013
cited By 7; International audience; Templated assembly of organic molecules constitutes a promising approach for fabricating functional nanostructures at surfaces with molecular-scale control. Using the substrate template for steering the adsorbate growth enables creating a rich variety of molecular structures by tuning the subtle balance of intermolecular and molecule–surface interactions. On insulating surfaces, however, surface templating is largely absent due to the comparatively weak molecule–surface interactions compared to metallic substrates. Here, we demonstrate the activation of substrate templating in molecular self-assembly on a bulk insulator by controlled deprotonation of the …
How Hydrogen Bonds Affect Reactivity and Intervalence Charge Transfer in Ferrocenium‐Phenolate Radicals
2016
The ferrocenyl-phenol 2,4-di-tert-butyl-6-(ferrocenylcarbamoyl)phenol (H-1) forms intramolecular hydrogen bonds which are absent in its constitutional isomer 2,6-di-tert-butyl-4-(ferrocenylcarbamoyl)phenol (H-2). Their corresponding bases 1– and 2– show intra- and intermolecular NH···O hydrogen bonds, respectively. The phenolate 1– is reversibly oxidized to 1·, whereas 2– only undergoes a quasi-reversible oxidation to 2·, which suggests a higher reactivity. The radical pools of 1· and 2· formed by the oxidation/deprotonation of H-1 and H-2 have been probed by (rapid-freeze) electron paramagnetic resonance (EPR) spectroscopy and by spin-trapping techniques to elucidate the types of radicals …
Kinetic and equilibrium studies for the adsorption of acid nucleic bases onto K10 montmorillonite
2011
Abstract The kinetic of the adsorption of two nucleic acid bases, namely adenine (A) and cytosine (C), on K10 montmorillonite (MMT) clay has been investigated over a wide range of nitrogenous bases concentrations, by using the spectrophotometric method. The measurements have been performed at T = 25.0 °C and pH = 4.0 where adenine and cytosine exist both in their protonated and neutral forms. Preliminary to the kinetic data treatment, the adsorption isotherms have been gathered and, then, analyzed by using the Freundlich and the Dubinin–Radushkevich model. The obtained results allow to draw the conclusion that physisorption of adenine and cytosine on MMT occurs and the process is mainly gov…
Syntheses with organoboranes. Part 14: Enolization–aldolization of conjugated cyclohexenones via dienolborinates
2002
Abstract Enolization of cyclohex-2-enone ( 1 ), 3-methyl- ( 2 ), 3,5-dimethyl- ( 3 ), 3,5,5-trimethyl- ( 4 ), and 3,4,5,5-tetramethylcyclohex-2-enone ( 5 ) with chlorodicyclohexylborane proceeds by deprotonation at the 6-position. Aldolization of the dienolborinates with benzaldehyde, and acetaldehyde, provides the corresponding anti aldols with 87–95% selectivity. Ketones 4 and 5 undergo competitive deprotonation at the 3-methyl group and aldolization at the 2-position. In contrast, lithium dienolates derived from 4 and 5 gave syn aldols with 95% selectivity.
Synthesis of an enantiopure 2-arylcyclohexanols from prochiral enol acetates by an enantioselective protonation/diastereoselective reduction sequence
2003
Abstract The enantioselective protonation with 2-sulfinyl alcohols of lithium enolates of 2-arylcyclohexanones with different substituents on the phenyl group takes place with excellent enantioselectivities (89–99%). Chiral 2-phenylcyclohexanone and 2-arylcyclohexanones carrying electron donor substituents on the aromatic ring are converted into the corresponding trans -2-arylcyclohexanols by diastereoselective reduction with sodium naphthalenide in the presence of acetamide. The stereochemical integrity of the tertiary stereocenter is fully preserved using this reduction procedure. Interestingly, the chiral proton source is not consumed in the synthesis.
PREPARATION AND REACTIONS OF 2-PYRIDYLPLATINUM(II) COMPLEXES [PTCL(C5H4N-C2)(TERTIARY PHOSPHINE)2] - COMPOUNDS WITH A MARKEDLY NUCLEOPHILIC PYRIDINE …
1989
Abstract The 2-pyridyl complex trans -[PtCl(C 5 H 4 N- C 2 )(PPh 3 ) 2 ] (I) can be prepared in high yield by oxidative addition of 2-chloropyridine to [Pt(PPh 3 ) 4 ]. The reaction of I with 1,2-bis(diphenylphosphino)ethane yields the cis derivative [PtCl(C 4 5 H 4 N- C 2 )(dppe)] (II). In polar solvents, the latter rearranges to the binuclear cationic complex [Pt(μ-C 5 H 4 N- C 2 , N )(dppe)] 2 Cl 2 . The reaction of I with [PdCl(η 3 -2-MeC 3 H 4 )] 2 (1/0.5 molar ratio) gives the products [PtCl(μ-C 5 H 4 N- C 2 , N )(PPh 3 )] 2 (IV) and [PdCl(η 3 -2-MeC 3 H 4 )(PPh 3 )]. 31 P NMR monitoring of the reaction suggests that PPh 3 transfer occurs in a binuclear platinum/palladium intermediate…