Search results for "Alkylation"
showing 10 items of 219 documents
Synthesis of Sterically Hindered Chiral 1,4-Diols from Different Lignan-Based Backbones
2013
Methods for synthetic modifications of the natural dibenzylbutyrolactone lignan hydroxymatairesinol into chiral 1,4-diols with different lignan-derived backbones have been developed. A stepwise procedure, involving alkylation and oxidation, was shown to be successful and several highly substituted 1,4-diols were prepared. Some substituted butyrolactones resisted alkylation and led to the formation unusually stable hemiketals (butyrolactols). The formation of stable hemiketals was investigated in detail, showing that different backbone structures influence the formation and reactivity of the hemiketals.
N1-Functionalized Indole-Phosphane Oxazoline (IndPHOX) Ligands in Asymmetric Allylic Substitution Reactions
2012
N-Functionalized IndPHOX ligands bearing various groups have been synthesized and the effects of the N1-substituent on the reaction rate, yield, and asymmetric induction in a palladium-catalyzed allylic substitution reaction are reported. The presence of an oxygen atom in the ligands, namely an N-MOM or N-THP group, led to enhancement of the enantioselectivity in the allylic amination reaction. In addition, a ligand with a chiral oxazoline ring at C-1 and a phosphane substituent at C-2 provided high enantioselectivity in good yield in an asymmetric allylic alkylation reaction.
Metalation and N-alkylation of some polyamides
1981
Totally N-substituted polyamides were synthesized starting from poly(2,4,4-trimethylhexamethylene terephthalamide) by metalation of the amide groups and subsequent reaction with several electrophiles. Polyamides of this structure are not available from terephthalic acid and the corresponding diamines by polycondensation. This N-alkylation reaction can be used for the synthesis of comb-like graft copolymers. The solubilitity and the thermal properties of these polyamide derivatives are described.
Reaktionen von elektronenreichen Heterocyclen mit Orthocarbonsäure-Derivaten, 10. Formylierungs- und Alkylierungsreaktionen von Carbazolen mit ambide…
1987
Carbazole werden durch Diethoxycarbenium-tetrafluoroborat mit hoher Regioselektivitat formyliert, wahrend die thermodynamisch stabileren Diethoxymethylcarbenium- und Trimethoxycarbenium-Ionen infolge ausgepragter ambidenter Elektrophilie Carbazole bevorzugt alkylieren. Reactions of Electron-Rich Heterocycles with Orthocarboxylic Acid Derivatives, 10. – Formylation and Alkylation of Carbazoles with Ambident Dialkoxycarbenium Tetrafluoroborates Carbazole and some derivatives were formylated regioselectively with diethoxycarbenium tetrafluoroborate. The thermodynamically more stable diethoxymethylcarbenium and trimethoxycarbenium ions exhibit ambident electrophilic reactivity as predominant al…
Recyclable Heterogeneous and Low-Loading Homogeneous Chiral Imidazolidinone Catalysts for α-Alkylation of Aldehydes
2014
Two polystyrene-supported and six homogeneous MacMillan imidazolidinone catalysts were prepared and tested for the asymmetric α-alkylation of propanal with benzodithiolylium tetrafluoroborate. The chiral imidazolidinone was linked to polystyrene through the N-3 atom or through the phenyl ring and their catalytic activity was compared with that of their unsupported precursors. This comparison has allowed us to find an unsupported catalyst that displays high catalytic activity down to 5 or 2 mol % at room temperature with a high level of enantioselectivity also when used with hexanal and 3-phenylpropanal. In addition, one of the heterogeneous materials was revealed to be highly recyclable for…
Enantioselective Zirconium-Catalyzed Friedel−Crafts Alkylation of Pyrrole with Trifluoromethyl Ketones
2009
The first catalytic enantioselective Friedel-Crafts alkylation of pyrrole with 2,2,2-trifluoroacetophenones to give pyrroles with a trifluoromethyl-substituted tertiary alcohol moiety bearing a quaternary stereogenic center is described. The reaction is achieved in the presence of a 3,3'-dibromo-BINOL-Zr(IV) complex to give the expected products with high yields (up to 98%) and good enantioselectivities (up to 93% ee). The absolute stereochemistry of the products has been determined by chemical correlation.
Synthesis, Structural Characterisation and Reactivity of New Dinuclear Monocyclopentadienyl Imidoniobium and ‐tantalum Complexes − X‐ray Crystal Stru…
2004
The preparation of a family of dinuclear monocyclopentadienyl imidoniobium and -tantalum complexes was achieved by two different synthetic routes. The diimido complexes [{M(Cp′)Cl2}2(μ-1,i-NC6H4N)] [Cp′ = η5-C5H4SiMe3, M = Nb, i = 4 (1); Cp′ = η5-C5H4SiMe3, M = Nb, i = 3 (2); Cp′ = η5-C5H4SiMe3, M = Nb, i = 2 (3); Cp′ = η5-C5Me5, M = Nb, i = 4 (4); Cp′ = η5-C5Me5, M = Nb, i = 3 (5); Cp′ = η5-C5H4SiMe3, M = Ta, i = 4 (6); Cp′ = η5-C5H4SiMe3, M = Ta, i = 3 (7)] were prepared by the reaction of one equivalent of the trichloro precursor [{MCl3}2(μ-1,i-NC6H4N)] (M = Nb, Ta, i = 4, 3 or 2) with two equivalents of either C5H4(SiMe3)2 or C5Me5(SiMe3). Complexes 1−7 can also be prepared by the react…
Acid Catalysis with Alkane/Water Microdroplets in Ionic Liquids
2021
Ionic liquids are composed of an organic cation and a highly delocalized perfluorinated anion, which remain tight to each other and neutral across the extended liquid framework. Here we show that n-alkanes in millimolar amounts enable a sufficient ion charge separation to release the innate acidity of the ionic liquid and catalyze the industrially relevant alkylation of phenol, after generating homogeneous, self-stabilized, and surfactant-free microdroplets (1–5 μm). This extremely mild and simple protocol circumvents any external additive or potential ionic liquid degradation and can be extended to water, which spontaneously generates microdroplets (ca. 3 μm) and catalyzes Brönsted rather …
Highly Enantioselective Friedel−Crafts Alkylations of Indoles with Simple Enones Catalyzed by Zirconium(IV)−BINOL Complexes
2007
Complexes of BINOL-based ligands with Zr(OtBu)4 catalyze the Friedel-Crafts alkylation reaction of indoles and pyrrole with nonchelating beta-substituted alpha,beta-enones at room temperature affording the expected products with good yields and ee above 95% in most of the studied examples.
ChemInform Abstract: Enantioselective Synthesis of Tertiary Alcohols Through a Zirconium-Catalyzed Friedel-Crafts Alkylation of Pyrroles with α-Ketoe…
2011
Chiral complexes of 1,1′-bi-2-naphthol-based ligands with zirconium tert-butoxide catalyze the Friedel–Crafts alkylation of pyrroles with α-ketoesters to afford tertiary alcohols in good yields and ee up to 98%. The reaction is also of application to 4,7-dihydroindole to give C2-alkylated indoles after oxidation with p-benzoquinone.