Allylamines carbonylation

Allylamines are not easily cleaved with Pd catalysts, but the carbonylation of the allylic amine 395 proceeds at 110 C to give the /3,7-unsaturated amide 396 by using dppp as a ligand[252], Dccarboxylation-carbonylation of allyl diethyl-carbamate under severe conditions (100 C, 80 atm) affords /3,7-unsaturated amides[2531. The 3-vinylaziridine 397 is converted into the a-vinyl-J-lactam 398 under mild conditions[254]. 

In one example, carbonylation of allylamine catalyzed by rhodium phosphine (1,4-diphos) gave a dihydropyr-... 

The simple procedure for the carbonylation of allyl halides has been extended in the high yielding solid-liquid two-phase conversion of allyl phosphates into amides (60-80%) under the influence of a rhodium carbonyl cluster in the presence of primary or secondary amines (Scheme 8.8). A secondary product of the reaction is the allylamine, the concentration of which increases as the pressure of the carbon monoxide is reduced, such that it is the sole product (ca. 80%) in the absence of carbon monoxide [28],... 

Carbonyl reagents, such as semicarbazide and phenelzine (27), are inactivators of SSAO. In a strategy that includes two inactivating structural motifs (allylamine and hydrazine), a series of allyl hydrazines including the series 28a-c as well as the fluoroallyl analogue 29 were prepared. Compounds 28a-c were potent irreversible inhibitors of SSAO, and compounds 28a,c had particularly good selectivity with respect to MAO inhibition. The presence of the vinyl fluoride in 29 had little effect on potency but did result in a loss in selectivity [82]. 

Aminoallyl carbanions, obtained by deprotonation of enamines or allylamines, are well-known homoenolate equivalents, since electrophilic attack occurs, in most cases, highly regiose-lectively to give the 3-substituted enamines, hydrolysis of which leads to the corresponding carbonyl compounds15 24,25. 

Type IV (spectators to CM) 1,1-Disubstituted olefms " 1,1-Disubstituted olefms, disub. o ,/ -unsaturated carbonyls, 4° allylic carbon-containing olefins, perfluorinated alkane olefins, 3° allylamines (protected)" Vinyl nitro olefins, protected trisubstituted allyl alcohols, a,/ -olefin of 2-subst. 1.3- butadienes, a,/ -olefm of electronically deactivated 1.3- butadienes ... 

Allylamines cyclize readily with a dicobalt octacarbonyl catalyst (equation 55).1,2 Rhodium catalysis generally allows the carbonylative cyclization to be carried out under milder conditions.86 Application of this reaction to unsaturated amides yields the corresponding imides, the best yields arising when R1 = H and R2 = allyl (equation 56).I>2... 

Iron carbonyls have been used in stoichiometric and catalytic amounts for a variety of transformations in organic synthesis. For example, the isomerization of 1,4-dienes to 1,3-dienes by formation of tricarbonyl(ri4-l,3-diene)iron complexes and subsequent oxidative demetallation has been applied to the synthesis of 12-prostaglandin PGC2 [10], The photochemically induced double bond isomerization of allyl alcohols to aldehydes [11] and allylamines to enamines [12,13] can be carried out with catalytic amounts of iron carbonyls (see Section 1.4.3). 

Metalated Hydrazones, Formamides, Allylamines, and Aminonitriles in "Current Trends in Organic Synthesis", Nozaki, H., Ed. Pergamon Press Oxford, 1983 p. 151 (d) Enders, D. "Asymmetric Synthesis of Carbonyl Compounds and Primary Amines" in Selectivity - a Goal for Synthetic Efficiency", Bartmann, W. Trost, B. M., Eds. Verlag Chemie Weinheim, 1984 p. 65. (e) Enders, D. Chemiaa Seripta 1985, 25, 139. 

Alkenyl aziridines are useful synthetic building blocks and can be converted to allylamines by conjugate addition of organocuprates [29], to pyrroline derivatives by rearrangement [30] and to P-lactams by Pd-catalyzed carbonylation [31]. 

Aza-Cope rearrangement.7 This reaction proceeds readily when catalyzed by Pd(0) and a strong protic acid, particularly trifluoroacetic acid or methanesul-fonic acid. This isomerization is involved in a direct synthesis of S,e-unsaturated imines from allylamines with carbonyl compounds (equation I). The unsaturated... 

The most frequently performed reaction with organometals concerns the well-known addition to the carbonyl group of ketobases. This reaction (Fig. 114) exhibits many affinities with reduction, as it affords an aminoalcohol (296), in this case tertiary, and involves analogous stereochemical features when chiral ketobases are employed. Again, the aminoalcohols produced can be further converted, by dehydration, into allylamines (R R C=CH—CHi—N<), which are useful in pharmaceutical chemistry. - ... 

Transformation of allyl alcohols and allylamines to y,6-unsaturated carbonyl compounds 855... 

Carbonylation of allylamines can produce pyrrolidones, although relatively high pressures of CO are usually required. Homogeneous rhodium catalysts are preferred and, using similar catalysts, the pyrrolidones can be obtained from allylic halides, CO and ammonia (Scheme 28). ... 

Dialkyl cyanomethylphosphonates are routine reagents readily accessible on laboratory scale and also available from a number of chemical suppliers. Since the review by Pudovik and Yastrebova published in 1970, ° the use of dialkyl cyanomethylphosphonates in Homer-Wadsworth-Enunons reactions has been covered in several comprehensive and excellent reviews. AU the factors governing the reaction (nature of the carbanions and carbonyl group, reaction conditions, mechanism, and stereochemistry) have been studied in depth. We invite the reader to refer to these papers. In contrast, we discuss here the synthetic applications resulting directly from the use of dialkyl cyanomethylphosphonate, which is the pathway of choice for the preparation, via a,p-unsaturatcd nitriles, of a,P-unsaturated aldehydes, cyanoethyl compounds, allylamines, and saturated amines. 

Catalytic hydrogenation gives a mixture of partially reduced products (enamine and allylamine) and/or saturated amine depending on the conditions used . Partial reduction also occurs on treatment with lithium in ammonia . Dienamines are resistant to reduction by lithium aluminium hydride which therefore provides a means for selective reduction of a less reactive carbonyl group in polyfunctional molecules (Scheme 13). 

Imine anions obtained by isomerization of heterocyclic, secondary allylic amines with n-butyllithium add to benzophenone (Schemes 9 and lO). However, the generality of this process with respect to the allylamine starting material and the carbonyl partner remains to be established. 

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