Search results for "nucleophilic addition"
showing 10 items of 63 documents
A Convenient Generation of Acetic Acid Dianion
2003
The lithium enediolate of acetic acid can be generated efficiently, as a 0.5 M solution in THF, using lithium amides prepared from n-butyllithium in THF and either diethylamine or 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane (AZA). Its reaction with carbonyl compounds leads to the corresponding β-hydroxy acids in good to moderate yields. Better yields are usually obtained when these amines are added in sub-stoichiometric amounts. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Catalytic Asymmetric Formal [3+2] Cycloaddition of 2-Isocyanatomalonate Esters and Unsaturated Imines: Synthesis of Highly Substituted Chiral γ-Lacta…
2017
[EN] Unlike their isocyano and isothiocyanato analogues, isocyanato esters remain almost unexplored as formal 1,3-dipoles in asymmetric catalytic reactions. The first asymmetric formal [3+2] cycloaddition involving isocyanato esters and electrophilic alkenes is reported. Diisopropyl 2-isocyanatomalonate reacts with a,b-unsaturated N-(o-anisidyl) imines in the presence of a Mg(OTf)2¿BOX complex to give highly substituted chiral pyrrolidinones featuring a conjugate exocyclic double bond with excellent yields and enantiomeric excesses up to 99%. Several transformations of the resulting heterocycles, including the synthesis of a pyroglutamic acid derivative, have been carried out.
Enantioselective zinc/BINOL-catalysed alkynylation of aldimines generated in situ from α-amido sulfones.
2012
Chiral nonracemic N-Cbz-protected propargylic amines have been prepared by the addition of terminal alkynes to imines generated in situ from α-amido sulfones in the presence of diethylzinc and BINOL-type ligands as catalysts. The reactions give good yields and high enantioselectivities (ee values up to 95 %) for a good number of aromatic and heteroaromatic α-amido sulfones and alkynes.
Zum Mechanismus der Inden‐Bildung durch Friedel‐Crafts‐Cycloalkenylierung
1972
α,β-Ungesattigte Aldehyde reagieren mit Benzol unter Friedel-Crafts-Bedingungen zu Indenen. Mittels 14C- und 2H-indizierten Verbindungen werden die reversible, nucleophile Addition von Benzol an Zimtaldehyd sowie die 1.3-Wasserstoff-Verschiebung im Crotonaldehyd beim Ringschlus nachgewiesen. On the Mechanism of the Indene Formation by Friedel-Crafts Cycloalkenylation α,β-Unsaturated aldehydes were condensed with benzene in a Friedel-Crafts type reaction to give indenes. With the aid of 14C- and 2H-labelled compounds both the reversible nucleophilic addition of benzene to cinnamaldehyde and the 1.3-hydrogen shift in the cycloalkenylation of crotonaldehyde are examined.
Highly diastereoselective additions of organometallic reagents to 1-O-silylated 3,4-Di-O-benzyl-L-erythrulose derivatives
1993
Abstract The diastereoselectivity of the addition of several organometallic reagents to the carbonyl group of the title compounds has been investigated. Some organomagnesium reagents display high diastereoselectivities (90–99%) and the major products are those predicted by the α-chelation model.
Fluorinated Heterocyclic Compounds. An Effective Strategy for the Synthesis of Fluorinated Z-Oximes of 3-Perfluoroalkyl-6-phenyl-2H-1,2,4-triazin- 5-…
2005
The reaction of 3-benzoyl-5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine has been investigated, evidencing the possibility of competitive reaction paths. Nucleophilic addition of the hydrazine to the electrophilic C(5) of the 1,2,4-oxadiazole ring, followed by ring opening and ring closure with enlargement, leads with high yield and in very mild experimental conditions to the formation of Z-oximes of 3-perfluoroalkyl-6-phenyl-2H-1,2,4-triazin-5-ones (11a-c) as major products of the reaction. In turn, the hydrazine can attack the electrophilic carbonyl carbon giving 4-perfluoroacylamino-5-phenyl-2H-1,2,3-triazoles (13a-c) through the well-known Boulton-Katritzky rearrangement of the inter…
A DFT mechanistic study of the synthesis of trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl from addition of NH3 to trans-[PtIICl2(N CMe)2]
2020
Abstract The reaction mechanism between trans-[PtIICl2(N CMe)2] and ammonia to give trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl has been studied at DFT level. Results showed that, in dichloromethane solution at 263.15 K, the chloride substitution by the ammonia on platinum is a process kinetically more favoured than the ammonia nucleophilic addition to the nitrile of about three orders of magnitude, and hence the nucleophilic addition reaction occurs after. Finally, both nucleophilic addition steps are geometrically driven to give products in the E configuration even if the final products were experimentally observed in the Z configuration. For trans-Z,Z-[PtIICl(NH3)(N CMe)2, the isomerizatio…
Reaction between Indazole and Pd-Bound Isocyanides-A Theoretical Mechanistic Study
2018
The mechanism of the addition of indazole (Ind)&mdash
Tandem Nucleophilic Addition−Intramolecular Aza-Michael Reaction: Facile Synthesis of Chiral Fluorinated Isoindolines
2010
A highly stereoselective synthesis of fluorinated 1,3-disubstituted isoindolines is described. To this end, a tandem reaction consisting of a diastereoselective addition of fluorinated nucleophiles to Ellman's N-(tert-butanesulfinyl)imines followed by an intramolecular aza-Michael reaction has been developed. This strategy allows for the construction of isoindolines bearing several degrees of fluorination (mono-, di-, or trifluoromethyl as well as heavier fluorinated groups). In the majority of all cases, the products are formed as single isomers.
Mapping the fluorophilicity of a hydrophobic pocket: synthesis and biological evaluation of tricyclic thrombin inhibitors directing fluorinated alkyl…
2006
In the completion of our fluorine scan of tricyclic inhibitors to map the fluorophilicity/fluorophobicity of the thrombin active site, a series of 11 new ligands featuring alkyl, alkenyl, and fluoroalkyl groups was prepared to explore fluorine effects on binding into the hydrophobic proximal (P) pocket, lined by Tyr 60A and Trp 60D, His 57, and Leu 99. The synthesis of the tricyclic scaffolds was based on the 1,3-dipolar cycloaddition of azomethine ylides, derived from L-proline and 4-bromobenzaldehyde, with N-(4-fluorobenzyl)maleimide. Introduction of alkyl, alkenyl, and partially fluorinated alkyl residues was achieved upon substitution of a sulfonyl group by mixed Mg/Zn organometallics f…