Amine From unsaturated amide

Early attempts to extend the halolactonization procedure to yield lactams gave cyclic imidates instead, but several approaches favor lactam products. These include working with silyl imidates, imidate esters or oxazolines, using sulfonylcarbamates or other acidic amides or by using hydroxyl-amine derivatives with increased nucleophilicity due to the a-effect. Lactams can also be favored as a consequence of steric requirements. In a few cases, amines can be cyclized to cyclic amines many lead references are given in a recent report on cyclic hydroxylamines such as (64). Veiy recent work has provided a fairly general iodolactamization procedure from unsaturated amides, trimethylsilyl triflate and iodine (Scheme 89). ... 

The compositions consist of a heat-plastified mixture of an ethylene homopolymer or copolymer, about 3 to 30 pbw of an elastomer, a stability control agent, which is a partial ester of a long chain fatty acid with a polyol, higher allyl amine, fatty acid amide or olefinically unsaturated carboxylic acid copolymer, and a hydrocarbon blowing agent having from 1 to 6 carbon atoms and a boiling point between -175 and 50C. 

Photocyclization of a,/3-unsaturated amides (152) also gives /3-lactams. This proceeds by cleavage of the intermediate biradical (153) to give ketene and imine which recombine. A small amount of amide (154) results from reaction of the ketene with amine that is produced by hydrolysis of the imine. This type of photodealkylation detracts from the generality of the process (79JCS(P1)263, 77T485). 

Analogous to the use of chiral enoates (see previous section), a, -unsaturated carboxylic amides, prepared from chiral amines, may be utilized in asymmetric 1,4-additions. When Grignard reagents are added to unsaturated amides (21), derived from (-)-ephedrine (20),25 highly optically active fi-sub-stituted alkanoic acids (22 R and R = alkyl or phenyl) are obtained in a variety of cases, after hydrolysis of the initially formed adducts (Scheme 7). This method was used for the synthesis of the antibiotic (-) malyngolide and its stereoisomers.26 Recrystallization of the intermediate (saturated) amide was necess-... 

Utilization of a,(3-unsaturated amides derived from the chiral amine, namely, camphor sultam, has been made by several groups to test the feasibility of [l,3]dipolar cycloaddition reactions with these chiral systems. This methodology has been applied to the synthesis of (35,4/ )ethyl-l-azabicyclo[2.2.1]heptane-3-carboxylate (see above for non-specific syntheses).433... 

The formation of activated iminium intermediates derived from nitrogen heterocycles has been reported by Comins and co-workers.163,163a The activation of pyridine derivative with phenyl chloroformate provides pyridinium salt, which smoothly reacts with the zinc homoenolate (Equation (94)).163 163a 164 The reaction of unsaturated amide with Ph jC 1 BI 4 produces iV-acyliminium ions, which react with PhaZn in CH2CI2 producing the desired a--substituted amine (Equation (95)).165... 

Soai et al. investigated the effects of amines on the diastereoselectivity of the conjugate addition of butyllithium to the a,j -unsaturated amide 274, derived from the a-amino acid of S-proline. When DBU was applied as base, (-)-(/ )-3-phenylheptanoic acid (275) was obtained in 55% e.e. (83SC27). 

Plants of the Compositae, Piperaceae and Rutaceae families [2] have been used as ingredients in many medicinal preparations and as food spices and many of them are used as insecticides [6]. Several long-chain unsaturated amides have been isolated from these plants, and they can be classified into two main structural types (a) (2 , 4 )-dienamides derived from straight-chain fatty acids and isobutylamine, pyrrolidine or piperidine units (1-22) (Chart 1), and (b) amides with the piperonal unit derived mainly from piperic acid in combination with the above mentioned amines (23-34) (Chart 2). 

Enolphosphate phosphonates derived from perfluoroalkanoylphosphonates have a number of synthetic uses. Reactions of such compounds with nucleophiles such as amines or alcohols in the presence of catalytic amounts of tetrabutylammonium fluoride (tbaf) gave a,j5-unsaturated perfluorocarboxylic acid derivatives, presumably via a ketene type intermediate (equation 94) When a primary amine was employed as the nucleophile a,j -unsaturated amides were formed, which could be converted into fluorinated pyrimidi-nones by treatment with urea. On the other hand, butylcopper(I) reagent reduces such... 

The amides are characteristically straight-chain, usually unsaturated compounds, and many incorporate an aromatic group (frequently 3, 4 -methylenedioxyphenyl) at the terminus remote from the amide function. Amides with and without a distal aromatic group are frequently produced by the same plant. Isobutylamine, pyrrolidine and piperidine predominate as the amine components of the Piper amides, although other amide classes, e.g., -pentyl or isopentylamides may be occasionally encountered [6]. In the case of at least one Piper species, P. guineense, attention has been drawn to the existence, which is intuitively predictable, of geographic variations in the relative proportions of amide constituents found in a species [7]. 

Poor yields attend the conversion of P,y- and y,5-unsaturated amides to the corresponding unsaturated amines. Only 20% of the theoretical amount of l-amino-2-cycloheptene was obtained from 2-< cloheptene-1-carboxamide. A yield of less than 15% is reported in the preparation of 2,3,3-trimethyl-l-cyclopentenylcarbinylamine from 2,3,3-trimethyl-1-cyclopentenylacetamide." In the conversion of 2,2-dimethyl-3-methylenecyclopentanecarboxamide to the corresponding amine, the amine was isolated in a yield of only 40%."... 

Soai K, Machida H, Ookawa A. Asymmetric conjugate addition of Grignard reagents in the presence of tertiary amines to a,p-unsaturated amides derived from (5)-2-(l-hydroxy-l-methylethyljpyrrolidine or (S)-prolinol. J. Chem. Soc., Chem. Commun. 1985 469-470. 

Twenty six affinin analogs were synthesized by amidation from unsaturated acids with simple aliphatic amines and evaluated for their sensory properties, being affinin the most active compound [174]. 

Loh, T.P., Cao, G.Q., and Yin, Z. (1999) A new method for the synthesis of 3,Y-unsaturated amides from allylic carbonate catalyzed by palladium in the presence of carbon monoxide and amine Studies towards the total synthesis of antillatoxin. Tetrahedron Lett., 40, 2649-2652. 

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