Alkenes Allylamine

The 4-hydroxy-1-alkene (homoallylic alcohol) 81 is oxidized to the hetni-acetal 82 of the aldehyde by the participation of the OH group when there is a substituent at C3. In the absence of the substituent, a ketone is obtained. The hemiacetal is converted into butyrolactone 83[117], When Pd nitro complex is used as a catalyst in /-BuOH under oxygen, acetals are obtained from homoallylic alcohols even in the absence of a substituent at C-3[l 18], /-Allylamine is oxidized to the acetal 84 of the aldehyde selectively by participation of the amino group[l 19],... 

The facile cyclopalladation of allylamine proceeds due to a chelating effect of the nitrogen. In MeOH, methoxypalladation take.s place to give the five-mem-bered chelating complex 507[460). The CO Insertion takes place readily in EtOH, giving ethyl 3-methoxy-4-dimethylaminobutyrate (508) in 50% yield[461). The insertion of alkenes also proceeds smoothly, giving the ami-noalkenes 509[462],... 

Metal-catalyzed C-H bond formation through isomerization, especially asymmetric variant of that, is highly useful in organic synthesis. The most successful example is no doubt the enantioselective isomerization of allylamines catalyzed by Rh(i)/TolBINAP complex, which was applied to the industrial synthesis of (—)-menthol. A highly enantioselective isomerization of allylic alcohols was also developed using Rh(l)/phosphaferrocene complex. Despite these successful examples, an enantioselective isomerization of unfunctionalized alkenes and metal-catalyzed isomerization of acetylenic triple bonds has not been extensively studied. Future developments of new catalysts and ligands for these reactions will enhance the synthetic utility of the metal-catalyzed isomerization reaction. 

Bei einer Variante dieser Reaktion erhalt man N-geschiitzte primare Allylamine, indem man das l-Phenylseleno-2-alken in Methanol mit Chloramin-T oder mit Carbamid-saure-benzylester/N-Chlor-succinimid/Triethylamin umsetzt2,4, wie hier fur die Herstel-lung von 3-Methyl-3-(4-methyl-henzolsulfonylamino)-l-buten (88%) und (2R,3E)-4-(Be-nzyloxycarbonyl-amino)-2-penten (56%) formuliert. 

The cyclization of carbamate derivatives of unsaturated amines has proven synthetically useful. Cyclizations of carbamates of allylamines containing a terminal vinyl group give oxazolidinone products (equation 60 and Table 17, entries 1 and 2).99,161 Bromocyclizations of systems with a di- or tri-sub-stituted alkene often give mixtures of oxazolidinones and tetrahydrooxazinones,163 while cyclization of an A -cinnamyl carbamate with phenylsulfenyl chloride gave only the oxazolidinone product.163b,163c The stereochemistry of the cyclization of primary carbamates of either allylic or homoallylic amines is low... 

While route B has been observed and utilized by Wiberg to synthesize silenes (see Section I), route A has been found to occur when less bulky substituents are used. Tamao and coworkers prepared the heterocycles (e.g. 689) by intramolecular hydrosilylation of silylated allylamines and decomposed them in toluene solution at 204 °C311. From the thermolysis of 689 they obtained the corresponding tram alkene and the dimerization product 691. In the presence of Me3SiOEt the insertion product 690 was formed at the expense of the dimer 691 (equation 230). 

Structural studies on the mechanism of the THF-catalyzed vinylic lithiation of allylamine derivatives have been performed using 2D and diffusion-ordered NMR spectroscopy.10 NMR evidence has suggested that in THF the mixed aggregate has close contact between the alkene and the /S-CfG of n-BuLi, whereas in the absence of THF, the allyl chain appears to be pointed away from the nearest n-BuLi residues. 

Substituted bicyclo[ . 1.0]alkanes may also be obtained by condensation of secondary amines with 2-haloketones. A variety of nucleophilic reactions can be carried out on the intermediate cyclopropaniminium salt 116251 (Scheme 108). Competing alkene scission and cyclopropanation occurs on reaction of enamines with pentacarbonyl-chromium carbene complexes252 (Scheme 109). N-Silylated allylamines and their derived N-silylated enamines undergo rhodium or copper catalysed cyclopropanation by methyl diazoacetate253 (Scheme 110). 

Lusinchi [11] illustrated the utility of the soluble polymer by examining both the reaction of immobilized xanthates with acceptors in solution and the reaction of immobilized alkenes with xanthates in solution. Firstly, immobilized xanthate 69 was prepared by chloroacetylation of 68, followed by displacement of chloride with 0-ethyl xanthate (Scheme 16). Treatment of 69 with excess protected allylamine 70 in the presence of 40 mol % lauroyl peroxide gave, after acid cleavage and coliunn chromatography, adduct 71 in good overall yield. Although H NMR indicated that the immobiUzed xanthate 69 was entirely consumed in the reaction, by-products were obtained due to the product xanthate formed on radical addition reacting further. 

The reaction of terminal epoxides with hindered lithium amide bases followed by organometallic reagents generates alkenes <2004JA12250>. Related reactions are the formation of enamines <2004JA6870> from terminal epoxides, 2-ene-l,4-diols from terminal epoxides <20050L2305>, and allylamines from amino epoxides <20060L349>. 

Early findings by Heck et al. revealed that coupling reactions of haloalkenes 90 with alkenes 89 in the presence of secondary amines gave allylamines [76a, 179] (Scheme 3-26 96/97 Nu = NR2). Based on this observation, inter-inter- as well as intra-intramolecular... 

A preparative method for allylamines is based on the Pd-catalyzed substitution reaction of /V-allylbenzotriazoles by amines. Formic acid is a convenient hydride source for allylic deoxygenation of Baylis-Hillman adducts via their derived acetates, thus the reaction is the conclusion of a three-step process for access to trisubstituted alkenes which contain one electron-deficient group. 

Allylamines An ene-type reaction between the reagent NsN=Se=NNs (prepared from NsNHNa, NsNCIj, and Se) and an alkene at room temperature gives the allylic sulfonamide. Under similar conditions, 1,3-dienes afford l,2-diamino-3-alkenes. 

Allylamines. Amines are allylated by alkenes (with double-bond transposition) ii an Mo-catalyzed reaction with t-BuOOH. 

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