Allylic Amides Research Articles

Intramolecular ene-type reaction between a diene–Fe(CO)3complex and alkene units

Heating of allylic amide or allylic ester substituted diene–Fe(CO)3 complexes such as (7) and (10)(140 °C) results in an intramolecular coupling of the pendant double bond with the diene moiety to give spirolactam and spirolactone derivatives; the stereochemical course of this reaction was established by an X-ray crystal structure determination of the lactone derivative (11).

Direct N-Allylation of Amides with 2-Allylisourea Catalyzed by Palladium(0)

Abstract Direct N-allylation of amides catalyzed by palladium(0) complexes took place under neutral conditions by the use of 2-allylisourea as the allylating agent.

Alkenylcopper Derivatives; 211,2. Synthesis of Allylic Amides and Amines by Amidomethylation of Alkenyl-Copper and -Cuprate Reagents

Reaction des dialcene-1yl-cuivre-lithium et des composes d'addition entre des alcene-1yl-cuivre-MgBr 2 , avec le [chloromethyl methyl] amide de l'acide formique et avec le N-chloromethyl phtalimide

ChemInform Abstract: THE REGIOSPECIFIC PHASE TRANSFER CATALYZED REDUCTIVE CARBONYLATION OF AZADIENES

AbstractIn einer regiospezifischen Reaktion setzen sich die Azadiene (Ia)‐(Id) mit Co‐ Carbonyl, CO und Methyliodid unter Phasentransferkatalyse zu den allylischen Amiden (II) und den Nebenprodukten (III) um.

The regiospecific phase transfer catalyzed reductive carbonylation of azadienes

Reaction of an azadiene with cobalt carbonyl, carbon monoxide, and methyl iodide under phase transfer catalysis conditions (benzene, water or aqueous NaOH, benzyltriethylammonium chloride) affords allylic amides in reasonable yields. This regiospecific reaction is sensitive to the concentration of base. One can also effect this transformation using acidic catalysis. A mechanism is proposed for the reductive carbonylation reaction.

Regio- and stereospecific synthesis of n-allyl amides by the horner-wittig reaction

E and Z allyl amides are formed with full regio- and stereochemical control from dianions of β- (acylamino) alkylphosphine oxides by the Horner-Wittig reaction.

Amidoselenation of olefins and its utilization for synthesis of allylic amides

Amidoselenation of olefins and its utilization for synthesis of allylic amides

Imine Anions Derived from 2° Allylic Amines

Abstract The application of allylic carbanions to organic synthesis is extensive2,3 and among the numerous variations are the generation and use of heteroallylic dianions. Noteworthy in this useful option is the ability of sulfide (−Sθ) to stabilize a developing adjacent carbanion,4,5 while alkoxide (−0θ) uniquely directs carbanion formation to a distal allylic position (Scheme I).6,7 We now wish to report that under conditions typically used for hetero allylic dianion formation 2° allylic amides provide a third reaction pathway for this structural entity by isomerizing to the resonance-stabilized imine anions (Scheme I).8,9 This overall conversion (presumably through an intermediate dianion) represents a heretofore unknown isomerization process that provides an alternative method for the generation of synthetically useful enolate equivalents.10

A versatile method for carbon-nitrogen bond formation via ene reactions of acylnitroso compounds

The use of acylnitroso compounds of the general formula RCONO as enophiles in the formation of carbon-nitrogen bonds is described. Both inter- and intramolecular ene reactions have been studied. For the intermolecular examples, nitrosocarbonylmethane, thermally liberated from its Diels-Alder adduct with 9,10-dimethylanthracene, is reacted with various olefins giving the corresponding N-alkylhydroxamic acids in moderate to high yields, providing an efficient method for allylic amidation. The regiochemistry of the intermolecular reaction is observed to be the result of kinetic control, and the direction of addition is consistent with attack by the olefin on electron-deficient nitrogen. Several examples of intramolecular ene cyclization are demonstrated, providing efficient entry into both spiro and fused bicyclic nitrogen containing systems which can be viewed as derived from annulation of 5- and 6- membered nitrogen containing rings onto 5- and 6-membered carbocycles, respectively. Various examples of this hetero-annulation scheme are described. Experimental details are also privided describing typical reaction procedures.

Selenoxide fragmentation leading to allylic amides

Selenoxide fragmentation leading to allylic amides

Allylic amidation. An investigation of nitrosocarbonylmethane for direct allylic functionalization of olefins

Nitrosocarbonylmethane reacts with a variety of olefins via an ene pathway, yielding N-substituted hydroxamic acid products in a preparatively useful reaction. With unsymmetrical olefins, observed regiochemical preferences can be rationalized by a mechanism involving electrophilic addition of nitrogen to the olefin.

ChemInform Abstract: STEREOSPECIFIC SYNTHESIS OF ALLYL AMIDES BY THE CYANOBORATE PROCESS

AbstractDie Dialkylborane (I) bilden mit den Alkinen (II) die Addukte (III), die mit Kaliumcyanid die Cyanoborate (IV) liefern.

Stereospecific synthesis of allyl amides by the cyanoborate process

Vinyl groups are shown to migrate readily, with retention of configuration, in the cyanoborate process leading to intermediates that are easily hydrolysed to sterically defined allyl amides.

Mercurated amides of alpha‐amino acids

Naturally‐occurring α‐amino acids have been employed in the preparation of a series of mercurated allyl amides as possible diuretics with low toxic and irritant properties. Relatively stable, recrystallizable and water‐soluble mercurials were isolated which showed diuretic activity either by intravenous or oral administration.