Diamination reactions

The overall process of this transformation was the subject of a detailed study [32]. It revealed that the reaction is reminiscent of the stereochemical pathways outlined above for aminoacetoxylation reactions, hence consisting of a syn-aminopalladation with an anti-C—N bond formation as the second step. The first step was found to be rate-determining, while the final one was suggested to involve a palladium(IV) catalyst state. 

The intramolecular diamination of alkenes could be further extended to the synthesis of cyclic guanidines (Eq. (4.29)) [31]. In this case, copper chloride represents the optimum oxidant and the reaction proceeds equally well for both five and six-membered annelation products. 

Although a rather new field of research, palladium-catalyzed 1,2-difunctionalization reactions have recently gained momentum. Major advances in this area have introduced suitable reactivity to incorporate chloride, bromide, oxygen and nitrogen-based nucleophiles into carbon frameworks. The common key step of all these transformations relies on the inter- or intra-molecular functionalization of intermediary alkyl-palladium bonds, for which several methods have been developed. The potential of all these approaches for organic synthesis is obvious, and the future looks bright for further developments in this field. 

Coleman, J.L., Hegedus, L.S., Noton, J.R., and Finke, R.G. (1987) Principles and Applications of Transition-Metal Chemistry, University Science Books, Mill Valley. For the concept of palladium(lV) chemistry Canty, A.J. (1992) Acc. Chem. Res., 25, 83. 

Fora review on Pd(IV) catalysis Muniz, K (2009) Angew. Chem. Int. Ed., 48, 9412. For the conceptual introduction of transient palladium oxidation with CuCh (a) Stangl, H. and Jira, R. (1970) 

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Polyetherimide synthesis has been achieved by reaction of a dianhydride containing an ether linkage with a diamine, reaction of a diamine containing an ether linkage with a dianhydride, or nucleophilic displacement of halo or nitro groups of a bisimide by bisphenol dianion (19,20). Such Pis exhibit good thermal stabiUty and melt processibiUty. 

A few scattered examples of hexahydro- and octahydro-l,3-diazocines have been reported, mainly in the context of studies on the effect of chain length on the cyclization of diamines. Reaction of the N- aryl-iV - aroyldiamines (194) with polyphosphoric ester gives the cyclic amidines (195) (77JCS(P2)2068). Yields of the diazocines (195 n =5) were about 40%, compared to 90% for the 1,3-diazepine (195 n =4). The basicities of the products decrease in the order of ring size 6 7>8 5, lower basicity reflecting non-planarity of the amidine system. 

The observed variations in the reactivities of the primary and secondary amino groups result in a shift of the gel point in the diepoxide-diamine reaction towards higher conversions by 4 % at the most (Fig. 3). If the substitution effect is not operative, the critical gel point is equal to 0.577 (Fig. 3). The remaining structural characteristics... 

Typical rheological curves obtained during a diepoxy-diamine reaction are shown in Fig. 6.3. The cure temperature (T = 90°C) is well above the glass transition temperature of the fully cured network (Tgoo 35°C), which means that only gelation occurs. Three typical regions are observed during cure (Matejka, 1991). 

Cu(I)-Cu(II) Catalysis Diamination Reactions Triggered by Diaziridinone Ring... 

Recently the diamination reaction of alkenes attracted much attention (reviews [377, 378]). Shi and coworkers disclosed a versatile palladium-catalyzed intermo-lecular diamination methodology [379]. For dienes, this process is selective for the internal double bond and occurs according to a classical two-electron catalytic... 

Fig. 74 Mechanistic divergence of copper(I)-catalyzed diamination reactions...

Fire resistant polymers were obtained from brominated epoxynovolak resin, BPA/DC prepolymer, BMI, Zn acetate and benzoyl peroxide [103] or from an oligo-aspartimide (BMI-diamine reaction product), BPA/DC, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane (i.e. Tetrabromo-Bisphenol A) and 2-ethyl-4-methylimi-dazole [104]. A mixture of BPA/DC, BMI and epoxide resin with brominated polycarbonate, copoly[oxy-2,6-dimethylphenylene)-(oxy-2,3,6-trimethylphenylene)] and a catalyst was also suggested [105],... 

Oxyamination and Diamination Reactions with Imido Osmium Complexes... 

Muniz K. Imido-osmium(VIII) compounds in organic synthesis I. Aminohydroxylation and diamination reactions. Chem. Soc. Rev. 2004 33 166-174. 

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