Amines allylamine

When solutions of the allyl phenyl telluroxides were treated at 65° with anilines, piperidine, primary aliphatic amines, or secondary aliphatic amines, allylamines were obtained in yields ranging from 15 to 95 %3. 

Effects of additives in the isomerization of substrate 45 by catalyst 17 were studied under the conditions of [S]=0.24 mol L [S] [C] =100 at 60 °C in THE The results are briefly summarized in Table 1, and are important both for mechanistic studies and improvements of the catalyst activity. Simple tertiary amines retard the reaction drastically, which suggests the coordination order of amines to Rh-BINAP species to be proportional with the order of basicity of simple tertiary amines, allylamines and enamines. Without the presence of simple tertiary amines, this phenomenon enables the fast replacement of the enamine formed from the catalyst by a substrate molecule that permits a smooth catalytic cycle. The presence of chelate diolefins like COD also disturbs the catalytic cycle. An over-isomerized by product, dienamine 44, acts as a strong catalyst poison. 

Amines also react with P-keto-esters to give the corresponding amino acid derivative. When 1.133 was treated with ethylamine in reaction 4, ethyl 3-(N-ethyl-amino)-3-phenylprop-2-enoate (1.134) was obtained. Several other 3-aryl derivatives (piperonyl, p-bromophenyl, p-methylphenyl, and p-nitrophenyl) were prepared by this method. The use of different amines (methylamine, isopropylamine, benzyl-amine, allylamine, aniline) led to several different N-substituted derivatives. ... 

Allylic amines are coupled to halides giving either allylic amines or enamines depending on the reaction condition. Reaction of steroidal dienyl triflate with Boc-diprotected allylamine affords allylamine. Use of AcOK as a base is crucial for the clean coupling[102]. The tert-allylic amine 123 reacts with an aryl halide to give the enamine 125 in DMF and allylic amine 124 in nonpolar solvents[103]. 

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]. 

Allylamines are difficult to cleave with Pd catalysts. Therefore, amines are protected as carbamates, but not as allylamines. Also, allyl ethers used for the protection of alcohols cannot be cleaved smoothly, hence alcohols are protected as carbonates. In other words, amines and alcohols are protected by an allyloxycarbonyl (AOC or Alloc) group. 

Allylamine. This amine can be synthesized by reaction of aHyl chloride with ammonia at the comparatively high temperature of 50—100°C (49), or at lower temperatures using CUCI2 or CuCl (51) as the catalyst. In aH such methods, a mixture of monoaHyl, diaHyl, and triaHyl amines is obtained. 

Formation of Amines. Mono-, di-, and triaEyl amines are prepared by reaction with ammonia. The ratio of reagents determines product distribution with sufficient time and excess of aEyl chloride, tetraaEylammonium chloride [13107-10-3] and triallylamine [102-70-5] predominate. Mixed amines are prepared in similar fashion by using a substituted amine in place of ammonia they may also be prepared with allylamine [107-11-9] and a suitable organic chloride. 

The initial anhydride concentration was about 3 x 10 M, and the amine concentration was much larger than this. The reaction was followed spectrophoto-metrically, and good first-order kinetics were observed hence, the reaction is first-order with respect to cinnamic anhydride. It was not convenient analytically to use the isolation technique to determine the order with respect to allylamine, because it is easier to observe the cinnamoyl group spectrophotometrically than to follow the loss of amine. Therefore, the preceding experiment was repeated at several amine concentrations, and from the first-order plots the pseudo-first-order rate constants were determined. These data are shown in Table 2-1. Letting A represent... 

Pd(dba)DPPB, 2-thiobenzoic acid, THF, 70-100% yield.Tertiary allyl-amines are cleaved efficiently at 20°, but secondary allylamines require heating to 60° to achieve cleavage. Thus, it is possible to monodeallylate a diallylamine by running the cleavage at 20°. "... 

The number of reactions that fit into this second class are manifold. Some typical examples are the amine-catalyzed reactions of 2,4-dinitrochlorobenzene with n-butylamine in chloroform (k"/k = 2.59 l.mole-1)23, with allylamine in chloroform (k"jk — 4.60 l.mole-1)24 and with allylamine in ethanol (k"fk =0.36 l.mole-1)25 and the amine-catalyzed reaction of p-nitrofluorobenzene with piperidine in polar solvents (k"/k < 3.2 l.mole-1)26. A typical example of a strongly catalyzed system is the reaction of 2,4-dinitrophenyl phenyl ether with piperidine in 60 % dioxan-40 % water27. 

Radical cyclization is compatible with the presence of other functional groups. Treatment of XCH2CON(R)-C(R )=CH2 derivatives (X = Cl, Br, 1) with Ph3SnH and AIBN led to formation of a lactam via radical cyclization. " Cyclization of N-iodoethyl-5-vinyl-2-pyrrolidinone led to the corresponding bicyclic lactam, " and there are other examples of radical cyclization with molecules containing a lactam unit " or an amide unit. Radical cyclization occurs with enamines as well. Photochemical irradiation of A,A-dialIyl acrylamide leads to formation of a lactam ring, and in this case thiophenol was added to generate the phenylthio derivative. Phenylseleno N-allylamines lead to cyclic amines. co-Iodo acrylate esters cyclize to form lactones. " ... 

In the synthesis of N heterocycles, this technique also overcomes competitive retro Michael addition that lowers the yield of 1,4-adduct in the Michael addition of amines to nitro olefins. Thus, a toluene solution of nitro olefin 159 was treated with allylamine 160, EtgN, and TMSCI under nitrogen at ambient tern-... 

It was possible to effect lOOC reaction leading to six-membered rings, e.g., 220 in low yield (ca. 20%) by heating the reaction mixture at 110 °C (Eq. 22) [59]. In fact, Oppolzer and Keller [60] had previously reported the lOOC reaction of 219 to 220 in 20% yield by heating at 110 °C. Furthermore, the scope of these oxime-olefin cycloadditions has been extended to ketoximes, e.g., 221. The latter was prepared by amination of a-bromoacetophenone with allylamine 214a. Heating of 221 at 110 °C for 8 h led to cycloaddition with formation of the fused pyrrolidine 222 in 88% yield. As in Scheme 25, only one... 

It has been found that DTBP cross-linking substantially increased the salt stability of the complexes. The salt stabilization is reversed upon the addition of DTT, which cleaves the bifunctional reagent, indicating that it is not due to the conversion of the amines to amidines and is dependent upon the cross-linking. Similar results were achieved with other polycations, including poly(allylamine), and histone HI. 

A-allylamine 23 (obtained by standard transformations of 6-iodogluco-side 22) underwent cyclization into the monocycle 24. However, when the amine was in situ protected as a Boc derivative it could be subjected to the RCM process. The products were further converted into the bicyclic aza sugar 26.19 A similar approach to eight-membered ring aza sugars was recently reported (Fig. 9).20... 

The Mannich reaction of secondary amines with paraformaldehyde and vinylboronic acids gives excellent yields of pure (E)-allylamines, e.g. equation 63181. 

Phosphorylated allenes 195 (R1 = H or Me) are a source of secondary ( )-allylamines. The allenes are treated with an amine R2NH2 (R2 = t-Bu or 4-MeCgH4 and the products, which exist as equilibrium mixtures of enamines 196 and imines 197, are olefinated by successive reaction with methyllithium and an aldehyde R3CHO (R = i-Bu, 4-MeCgH4, PhCH2CH2 etc). Reduction with sodium borohydride finally yields the... 

The joint action of primary or secondary amines (aniline, allylamine, benzylamine, butylmethylamine, iV-mcthylglycine methyl ester etc.) and copper bis(acetylacetonate) on the thiophen ylide 258 leads to dimethyl aminomalonates 259 by a carbene insertion reaction294. 

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