Morpholine proline

For both the in vitro studies with morpholine and pyrrolidine and the in vivo study with proline, it was observed that partially decomposed [Fe2(SMe)2(NO)4] was a much more potent nitrosation agent than the pure complex (110). The nature of the decomposition was not reported, and it is not clear what the significance of this report may be, although nitrite was probably present in the decomposed material. 

Prior to the work of Holladay and co-workers,38 there was good literature precedent for 4-keto-L-proline derivatives 39 giving the required 3,4-dehydro isomer of the enamine rather than the 4,5-dehydro isomer in a report by Friary and co-workers.46 It was found that the protected 4-keto-L-proline derivative 49 gave enamine 50 on treatment with morpholine in the presence of molecular sieves (Scheme 17). 

L-proline followed by reaction of the product with diethyl cyanomethylphosphonate (1, 250 2, 130-131) gives 2 and 3 in a 1 1 ratio (18.3% total yield). Use of piperidine acetate gives 2 and 3 in a 1 22 ratio (50.3% total yield). Dibenzylam-monium trifluoroacetate shows similar selectivity 2/3 = 1 19 (76.4% total yield). However, use of morpholine-camphoric acid in ether-HMPT favors formation of 2. With this catalyst 2 and 3,are obtained in 37.5% and 1.5% yield, respectively. ... 

ALDOL CONDENSATION (+)-(R)-l-Amino-2- methoxymethyl)pyrrolidine. Boron trichloride. Dialkylboron tri-fluoromethanesulfonates. Dibenzyl-ammonium trifluoroacetate. Di- -butylboryl trifluoromethanesulfonate. Dichlorodiethylaminoborane. Diiso-propylaluminum phenoxide. Diisopropyl-aminomagnesium bromide. Lithium diisopropylamide. Morpholine-Camphoric acid. Proline. 

Synthesis of Morpholin-2,5-diones via Diastereoselective Halolactonization Mediated by L-Proline Derivatives... 

A number of organocatalysts such as derivatives of proline and morpholine were screened by Barbas group and the tetrazole catalyst 26 gave the best result, with 95 % yield and 80 % ee. The enantiomerically enriched mixture could be recrystallized to yield 71 % of aminoaldehyde 27 in >99 % ee. 

Tetrapropylammonium perruthenate (TPAP 63 mg) was added in 1 portion to a stirred mixture of A -Boc-4-fra .y-hydroxy-L-proline (1 g, 3.47 mmol), A-methyl-morpholine A-oxide (0.62 g, 15.6 mmol), and powdered molecular sieves (4 A, 1.78 g) in CH2CI2 (7 mL) at room temperature under argon. The mixture was stirred for 3 h, filtered, and evaporated in vacuo to give a black residue. The product was purified by... 

Secondary amines and amino acids react in an entirely different way. Indeed, L-proline forms a mixture of the four possible tautomers, but, after a time, ninhydrin-positive substances may be formed by breakdown of the proUne molecule. (Other ketoses do not give this reaction.) Secondary amines, such as piperidine, will not react at 0°, but, at higher temperatures (40-60°), some D-fructosylamine is formed, together with a higher proportion of D-glucose by isomerization. Morpholine or dicyclohexylamine give a 20 to 25% yield of D-n6o-hexulose, and may be used on a preparative... 

Proline is a highly effective hgand for the Cul-catalysed displacement of bromine in 3-bromopyridines, 2-bromothiazoles and 5-bromo-l-phenylsulfonylindole by primary amines, morpholine and pyrazole. ... 

The deprotection of aloe derivatives of secondary amines such as N,N-benzylme-thylamine under the above conditions gave a substantial amount of the undesired allylamine [32], However, the use of a 40-fold excess of diethylamine as the jr-allyl scavenger led to the desired benzylmethylamine in quite good yield (Eq. 9). The formation of the undesired allylamine was also suppressed using a fivefold excess of diethylamine in a butyronitrile/water system. N-Allyloxycarbamates derived from secondary amines, such as morpholine, piperidine, proline, and ephedrine, reacted under the above-mentioned conditions at room temperature within 15 min to give the parent amines in quantitative yields without formation of the undesired allylamine. 

Gradl and Trauner recently reported the use of ketene N,N-acetals as precursors for the ketene N,0-acetal intermediate (Scheme 7.6) [llj. This version of the reaction allows for the incorporation of various amines, for instance morpholine or proline derivatives. The ketene N,N-acetals, e.g., 10, can be conveniently prepared by heating amide acetal 4 with higher boiling amines such as morphoUne. 

A number of derivatives of L-azetidine-2-carboxylic acid, a naturally occurring antimetabolite of proline, have been prepared. Its reaction with phenyl isothiocyanate gave the thiourea (187), which on treatment with dicyclohexylcarbodi-imide (DCC) formed 2-phenylimino-5-thiazolidinone (188). The thiazolidinone, which acylates morpholine at room temperature,... 

The group of P. Tremaine in Canada used a VTD for accuracy measuring (+0.01-0.04%) the high temperature volumetric properties of a number of electrolytes (Gd(Cp3S03)3, NaCp3S03, sodium tartrate dimethylammo-nium chloride, weak electrolytes (tartaric acid), non-electrolytes (methanol, morpholine, a-alanine, )5-alanine, and proline and mixtures of non-electrolytes and electrolytes (morpholinium chloride + HCl, dimethylammonium chloride + HCl). 

A related example disclosed recently by McNulty et al. is a one-pot Wittig reaction of aldehydes with phosphonium salts in the presence of 10 mol% of morpholine, L-proline or p-toluenesulfonamide and 2.0 equiv. of NaHCOs (Scheme 55) [227]. This reaction gives high E selectivity. A rapid and reversible condensation of the aldehyde with the amine (derivative) catalyst has been proposed to form an iminium or an imine intermediate that is subjected to olefination with the in situ generated phosphonium ylides, though a base-catalyzed pathway is not ruled out. It has been confirmed that an N-sulfonyl imine can be formed quantitatively from the corresponding aldehyde and sulfonamide under the reaction conditions. 

---