Epoxides, reaction with acid diamines

Oxidation of aliphatic C-H groups with HP is efficiently catalysed by cis-a-aminopyridine manganese complexes in the presence of acetic acid. The reaction demonstrated excellent efficiency (up to TON = 970), site selectivity, and stereospecificity (up to >99%). Manganese(II) and iron(II) complexes based on ligands with a rigid, chiral diamine derived from proline and two benzimidazoles (2) were synthesized and applied in epoxidation reaction with aqueous HP. Mn-complex catalyses the epoxidation of olefins. Isolated yields of 60-99% and up to 95% ee were obtained with 0.01-0.2mol% catalyst loading. The turnover frequencies and turnover numbers reached 59,000 h and 9600, respectively. Iron(II) complex exhibited a... 

Annual Volume 71 contains 30 checked and edited experimental procedures that illustrate important new synthetic methods or describe the preparation of particularly useful chemicals. This compilation begins with procedures exemplifying three important methods for preparing enantiomerically pure substances by asymmetric catalysis. The preparation of (R)-(-)-METHYL 3-HYDROXYBUTANOATE details the convenient preparation of a BINAP-ruthenium catalyst that is broadly useful for the asymmetric reduction of p-ketoesters. Catalysis of the carbonyl ene reaction by a chiral Lewis acid, in this case a binapthol-derived titanium catalyst, is illustrated in the preparation of METHYL (2R)-2-HYDROXY-4-PHENYL-4-PENTENOATE. The enantiomerically pure diamines, (1 R,2R)-(+)- AND (1S,2S)-(-)-1,2-DIPHENYL-1,2-ETHYLENEDIAMINE, are useful for a variety of asymmetric transformations hydrogenations, Michael additions, osmylations, epoxidations, allylations, aldol condensations and Diels-Alder reactions. Promotion of the Diels-Alder reaction with a diaminoalane derived from the (S,S)-diamine is demonstrated in the synthesis of (1S,endo)-3-(BICYCLO[2.2.1]HEPT-5-EN-2-YLCARBONYL)-2-OXAZOLIDINONE. 

Treatment with excess trifluoroacetic acid furnished the (dihydroiminoethano) carbazole 107 in 71% overall yield. Epoxidation of the alkene followed by a two-step protecting group modification gave epoxide 108, which underwent an oxidative epoxide opening followed by silyl protection to give silyl ether 109. Alloc deprotection, alkylation with (Z)-2-iodo-2-butenyl tosylate, followed by an intramolecular Heck reaction delivered pentacyclic diamine 110. A three-step formation of the p-ketoester 111 followed by a three-step reduction process afforded ester 112, which underwent a reduction and deprotection sequence to provide minfien-sine (99). A sequential catalytic asymmetric Heck-(V-acyliminium ion cyclization for the delivery of the enantiopure 3,4-dihydro-9a,4a-(iminoethano)-9//-carbazole is the highlight of the synthesis. 

Novel functionalized peroxides which may be used as UPR curing agents as well as initiators for polymerization reactions and as monomers for polymerizations to form peroxy-containing polymers were elaborated [162]. Initiators may be prepared by reacting hydroxy-containing tertiary hydroperoxides with diacid halides, dichloroformates, phosgene, diisocyanates, acid anhydrides and lactones to form the functionalized peroxides. These reaction products may be further reacted, if desired, with dialcohols, diamines, aminoalcohols, epoxides, epoxy alcohols, epoxy amines, diacid halides, dichloroformates and diisocyanates to form additional fimctionalized peroxides. The use of monoperoxyoxalates of the structure (Scheme 24) as initiators... 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

The axial immobilization of chiral [Mn((S,S)-salen )j (where salen = (Si,Sj-NiN -bis(3,5-diR -salicylidene)-l,2-diRbethane-diamine R = Bu, R -R = -(CH2)4- R = Bu, R = Ph R = Pn, R R = -(CH2)4-) complexes was achieved by reaction of [Mn(salen )Cl] with sulfonic acid- or phenol-substituted crosslinked and insoluble polystyrene resins [45]. The resulting polymer-immobilized [Mn(salen )j complexes were active and enantioselective for the asymmetric epoxidation of... 

Enantioselective epoxidation. This effective catalyst (1) is readily prepared in a 70-100 kg scale from the resolved diamine (with tartaric acid), the salicylaldehyde (from formylation of the phenol by Duff reaction), and manganese acetate, followed by anion exchange by treatment with aqueous NaCI. 

The transformation of this viscous liquid into a hard, cross-linked three-dimensional molecular network involves the reaction of the prepolymer with reagents such as amines or Lewis acids. This reaction is referred to as curing. The curing of epoxies with a primary amine such as hexamethylene-diamine involves the reaction of the amine with the epoxide. It proceeds essentially in two steps ... 

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