Allyl morpholine

The ylide obtained from (methyl)triphenylphosphonium bromide reacts with morpholine derivatives 597 to give phosphonium salts 598 which upon treatment with -butyllithium are converted to new ylides 599. In a reaction with aldehydes, ylides 599 form iV-(l,3-disubstituted allyl)-morpholines 602 (Scheme 94) <1996AQ138>. Another less common nucleophile that can be used for substitution of the benzotriazolyl moiety in Af-(a-aminoalkyl)benzotriazoles is an adduct of iV-benzylthiazolium salt to an aldehyde which reacts with compounds 597 to produce adducts 600. Under the reaction conditions, refluxing in acetonitrile, salts 600 decompose to liberate aminoketones 601 <1996H(42)273>. 

A reactor was charged with (E)-N-butenyl morpholine (0.81 mmol), titanium tetrachloride 2THF (8 JLmol), di-isopropylethylamine (1.22 mmol), propionyl chloride (0.98 mmol), and 8.1 ml CH2CI2 and the mixture stirred until the allylic morpholine was consumed as determined by TLC. Thereafter, the mixture was diluted with an equal volume of diethyl ether, washed with aqueous 1 M NaOH, dried, and the product isolated by chromatography on silica gel using diethyl ether in 92% yield. H- and C-NMR and HRMS (FAB) data supplied. 

Representative procedure for the gold-catalyzed intermolecular addition of amines to allenes. (E)-(3-(4-Methoxyphenyl)allyl)morpholin ... 

A chiral quaternary carbon center via an addition-rearrangement reaction of 3,3-disubstituted allyl morpholine (61) and benzyloxyacetyl chloride (56) was successfully constructed with 300 mol% of chiral Mgl2 (60) complex, and the corresponding Claisen adduct (62) was obtained in 97% ee and 94 6 syn anti selectivity (Scheme 4.18). 

Another method for deallylation of ally esters is the transfer of the allyl group to reactive nucleophiles. Amines such as morpholine are used[415-417], Potassium salts of higher carboxylic acids are used as an accepter of the allyl group[418]. The method is applied to the protection and deprotection of the acid function in rather unstable /f-lactam 664[419,420]. 

Pd(Ph3P)4, pyrrolidine, 0°, 5-15 min, CH3CN, 70-90% yield. Morpholine has also been used as an allyl scavenger in this process. ... 

That the methyl group in the less substituted isomer of the enamine (20) is axial was borne out by the work of Johnson et al. (18) in the total synthesis of the glutarimide antibiotic //-dehydrocycloheximide (24). The acylation of the morpholine enamine of 2,4-dimethylcyclohexanone (25) with 3-glutarimidylacetylchloride (26), followed by the hydrolysis of the intermediate product (27) with an acid buffer, led to the desired product in 35 % yield. The formation of the product in a rather low yield could most probably be ascribed to the relatively low enamine-type aetivity exhibited by the tetrasubstituted isomer, which fails to undergo the acylation reaction, and also because in trisubstituted isomer one of the CHj groups is axial. Since the methyl groups in the product are trans to each other, the allylic methyl group in the less substituted isomer of the enamine should then be in the axial orientation. 

Cyclohexanone, 2-allyl-, 42,14 Cyclohexanone, condensation with morpholine, 41, 65... 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

Morpholine also gives the allyhc amine in high yield. The reaction is thought to involve a known hydridopaUadium-catalyzed isomerization of alkynes to aUenes followed by reaction of the latter with the hydridopalladium complex to give 1-phenyl-substituted q -allylpalladium complexes. These complexes react with amines affording the allylic amines. Primary amines give the diallylic amines. An intramolecular version has been developed for the synthesis of 2-(2-phenyl)-pyrroUdines and -piperidines [319]. 

This allows for easy reuse of the catalyst in the reaction of allylation of secondary amines like piperidine or morpholine for several runs. The leaching of palladium was less than 0.001% of the initial amount. 

The supported aqueous phase methodology was applied to the system Pd(OAc)2/5 TPPTS, a catalytic precursor for the Trost-Tsuji reaction. The characterization of the solid by 31P MAS NMR confirms the presence of Pd°(TPPTS)3 as the main surface species. The catalytic properties of the solid were tested for the allylic substitution of E-cinnamylethylcarbonate by different nucleophiles such as ethyl acetoacetate, dimethyl malonate, morpholine, phenol, and 2-mercapto-pyridine. The absence of palladium leaching was demonstrated, and having solved the problem of water leaching from the solid to the organic phase, the SAP-Pd catalyst was successfully recycled several times without loss in its activity. It was used in a continuous flow experiment which... 

Another reaction performed in the dead-end reactor discussed before, is the allylic amination of 3-phenyl-2-propenyl-carbonic acid methyl ester with morpholine. [30] First and second generation commercially available DAB-dendrimers were functionalized with diphenylphosphine groups (Figure 4.13). Two different membranes were used, the Nadir UF-PA-5 (ultrafiltration) and the Koch MPF-50 (former SELRO) (nanofiltration), which gave retentions of 99.2% and 99.9% respectively for the second generation functionalized dendrimers. 

Removal of the Fmoc group was achieved by treatment with morpholine-dichloromethane, leaving the allylic anchor and the 0-glyco-... 

Syntheses of primary ally lie amines have been reviewed183. The regiochemistry of the reaction of iron carbonyl complexes with nucleophiles such as morpholine has been investigated. The (r 3-crolyl) Fe+(CO)4 BF4- complexes 172 (R1 = H R2 = Me or R1 = Me R2 = H) undergo preferential attack at the less substituted allyl terminus to yield allylic amines 173. The (/j2-crotyl acetate) Fe(CO)4 complex 174, on the other hand, does not react with morpholine184. 

C-terminal deprotection was performed using morpholine as an allyl trap, resulting in high yields. The most significant advantage of the allyl group in this peptide synthesis in comparison with the choline ester is that it overcomes the solubility problem encountered in the enzymatic deprotection approach. The deprotection of the allyl ester is performed in organic solvents, in which these lipidated peptide are readily soluble. ... 

EINECS 203-468-6, see Ethylenediamine EINECS 203-470-7, see Allyl alcohol EINECS 203-472-8, see Chloroacetaldehyde EINECS 203-481-7, see Methyl formate EINECS 203-523-4, see 2-Methylpentane EINECS 203-528-1, see 2-Pentanone EINECS 203-544-9, see 1-Nitropropane EINECS 203-545-4, see Vinyl acetate EINECS 203-548-0, see 2,4-Dimethylpentane EINECS 203-550-1, see 4-Methyl-2-pentanone EINECS 203-558-5, see Diisopropylamine EINECS 203-560-6, see Isopropyl ether EINECS 203-561-1, see Isopropyl acetate EINECS 203-564-8, see Acetic anhydride EINECS 203-571-6, see Maleic anhydride EINECS 203-576-3, see m-Xylene EINECS 203-598-3, see Bis(2-chloroisopropyl) ether EINECS 203-604-4, see 1,3,5-Trimethylbenzene EINECS 203-608-6, see 1,3,5-Trichlorobenzene EINECS 203-620-1, see Diisobutyl ketone EINECS 203-621-7, see sec-Hexyl acetate EINECS 203-623-8, see Bromobenzene EINECS 203-624-3, see Methylcyclohexane EINECS 203-625-9, see Toluene EINECS 203-628-5, see Chlorobenzene EINECS 203-630-6, see Cyclohexanol EINECS 203-632-7, see Phenol EINECS 203-686-1, see Propyl acetate EINECS 203-692-4, see Pentane EINECS 203-694-5, see 1-Pentene EINECS 203-695-0, see cis-2-Pentene EINECS 203-699-2, see Butylamine EINECS 203-713-7, see Methyl cellosolve EINECS 203-714-2, see Methylal EINECS 203-716-3, see Diethylamine EINECS 203-721-0, see Ethyl formate EINECS 203-726-8, see Tetrahydrofuran EINECS 203-729-4, see Thiophene EINECS 203-767-1, see 2-Heptanone EINECS 203-772-9, see Methyl cellosolve acetate EINECS 203-777-6, see Hexane EINECS 203-799-6, see 2-Chloroethyl vinyl ether EINECS 203-804-1, see 2-Ethoxyethanol EINECS 203-806-2, see Cyclohexane EINECS 203-807-8, see Cyclohexene EINECS 203-809-9, see Pyridine EINECS 203-815-1, see Morpholine EINECS 203-839-2, see 2-Ethoxyethyl acetate EINECS 203-870-1, see Bis(2-chloroethyl) ether EINECS 203-892-1, see Octane EINECS 203-893-7, see 1-Octene EINECS 203-905-0, see 2-Butoxyethanol EINECS 203-913-4, see Nonane EINECS 203-920-2, see Bis(2-chloroethoxy)methane EINECS 203-967-9, see Dodecane EINECS 204-066-3, see 2-Methylpropene EINECS 204-112-2, see Triphenyl phosphate EINECS 204-211-0, see Bis(2-ethylhexyl) phthalate EINECS 204-258-7, see l,3-Dichloro-5,5-dimethylhydantoin... 

In a subsequent paper (87), the same authors investigated the palladium-catalyzed allylic aminations with pyrphos-functionlized PPI and PAMAM dendrimers as multidentate ligands. Zero to four generation PPI-(pyrphosPdCl2)x and PAMAM-(pyrphosPdCl2)x neutral dendrimers (97) showed a strong positive dendritic effect on the selectivity of the allylic amination of 1,3-diphenyl-1-acetoxypropene with morpholine (at 45°C in DMSO). 

In the carbonylation reactions, further reaction of the acyl lithium compounds with carbon monoxide can occur, but clean reaction can be achieved if the lithium amide is first converted to a copper derivative (Scheme 130) (79JOC3734). In the case of morpholine, reaction with allyl bromide gave a 93% overall yield of the amide product. 

---