Ring opening reactions structure

Pyrazoles can be prepared by ring opening reactions of fused systems already containing the pyrazole nucleus. Thus several [5.5], [5.6] and [5.7] fused heterocycles have been opened to substituted pyrazoles, usually in basic medium. In general, the method has little preparative interest since another pyrazole derivative has usually been used to build the ring-fused system. However, due to the unexpected structures obtained, two publications are worthy of notice. 6//-Cyclopropa[5a,6a]pyrazolo[l,5-a]pyrimidine (638) was readily obtained from the corresponding pyrazolopyrimidine by the action of diazomethane at room temperature (Scheme 59) (81H(15)265). When (638) was treated with potassium hydroxide, the pyrazole (640) was formed, probably via the diazepine (639). 

As mentioned earlier, the possible products of the -complexes include ring-opened structures. This includes isomer 181 and some of its derivatives, for example, 187,188,196,197, 203, and 204, as well as the products of interaction with organoiron, 180,191, and 194, and organocobalt, 199,200, and 201, compounds. They have already been discussed together with the variously characterized V-complexes. Examples of the ring-opening reactions based on the -q- and ri -species are given next. 

The ring-opening reaction usually results in the formation of a new unsaturated linkage. When this is a carbon-carbon double bond, the further reaction of this group during polymerization leads to a crosslinked (and insoluble) structure and can be a serious problem when networks are undesirable. In many of the applications mentioned above, crosslinking is desirable. 

Karthikeyan S, Q Zhou, Z Zhao, C-L Kao, Z Tao, H Robinson, H-w Liu, H Zhang (2004) Structural analysis of Pseudomonas 1-aminocyclopropane-l-carboxylate deaminase complexes insight into the mechanism of a unique pyridoxal-5 -phosphate dependent cyclopropane ring-opening reaction. Biochemistry 43 13328-13339. 

To introduce intrinsic hydrophilicity into silicone like structures (necessary to provide wetting within high oxygen diffusion materials for contact lenses), the ring opening reaction by H20 addition was proved to be an adequate method (21) (Equation 6). 

Model computational studies aimed at understanding structure-reactivity relationships and substituent effects on carbocation stability for aza-PAHs derivatives were performed by density functional theory (DFT). Comparisons were made with the biological activity data when available. Protonation of the epoxides and diol epoxides, and subsequent epoxide ring opening reactions were analyzed for several families of compounds. Bay-region carbocations were formed via the O-protonated epoxides in barrierless processes. Relative carbocation stabilities were determined in the gas phase and in water as solvent (by the PCM method). 

One of the most efficient procedures for the synthesis of cyclopropanes is the reaction of alkenes with electrophilic carbene complexes. In this process up to three stereogenic centers can be generated in one step. Cyclopropanes are a key structural element encountered in many natural products with interesting biological activity. Further, by virtue of the ability of cyclopropanes to undergo ring-opening reactions these compounds can be valuable synthetic intermediates. 

The reactivity trend in terms of the ring-opening reaction for the series 43, 47, and 53 can be analyzed in terms of the geometries of imino and vinyl radicals. Most of the spin density in imino radicals is concentrated in the p-orbital on nitrogen, but vinyl radicals have a nonlinear, vp -like structure, where the spin density is in the i /j -orbital of the carbon. In the o-quinone diradicals 43,47, and 53, the / -orbitals of the nitrogens (accomodating the odd electrons) are better... 

The structural diversity (and complexity) of the products obtained by the MCR between tertiary isocyano amides, aldehydes, and amines could be increased to various heterocyclic scaffolds by combining the initial 2,4,5-tiisubstituted oxazole MCR with in situ intramolecular tandem processes (Fig. 17). Most tandem processes reported are based on the reactivity of the oxazole ring toward C=C or C=C bonds in hetero Diels-Alder reactions followed by ring opening reactions generating the rather complex heterocyclic products with high degrees of variation. 

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