Electronic effects on the stereoselectivity of epoxidation reactions catalysed by manganese porphyrins

A series of Mn(III) porphyrins progressively halogenated in the β- pyrrolic positions was employed to catalyse the epoxidation of cis-stilbene by iodosylbenzene, and to study the role of the electronic effects on the stereoselectivity of this process. A gradual improvement in the stereoselectivity on increasing the number of β-halogen atoms was observed. The role of steric effects upon the epoxidation was also investigated by placing ortho-substituents in the mesophenyl rings, and it was found that steric effects are more important than electronic effects toward the stereoselectivity of this process. These results can be rationalised by proposing a competition between a nonstereoselective electrophilic pathway of addition and a stereospecific pathway of oxygen insertion, the former being disfavoured by electron-withdrawing substituents. Alternatively, the formation of an open intermediate between the Mn(V) oxene and the substrate could be suggested, where the stereoselectivity ought to be determined by the competition between closure of the epoxide ring and rotation around the C-C bond. In this case, the enhanced stereoselectivity given by our polyhalogenated porphyrins might be attributed to an acceleration of the epoxide ring closure caused by the electron-withdrawing effect of the halogen substituents

Consensus Report by the Italian Academy of Osseointegration on the Use of Graft Materials in Postextraction Sites

Purpose: After tooth extraction, a modeling and remodeling phase of bone and soft tissues occurs. It has been fully demonstrated that bone resorption as high as 50% can take place regarding ridge width and a variable amount concerning ridge height, making it difficult to perform implant surgery. Materials and Methods: Active members of the Italian Academy of Osseointegration (IAO) participated in this Consensus Conference, and three systematic reviews were conducted before the meeting to provide guidelines on alveolar ridge preservation procedures. The systematic reviews covered the following topics: (1) What material best preserves the dimensions of the ridge horizontally and vertically?; (2) what material favors the formation of the highest quantity of new bone?; (3) which technique would best seal the socket?; and (4) what effect does alveolar ridge preservation have on soft tissues? Results: The main conclusions reached by the assembly were that alveolar ridge preservation is advisable after dental extraction, particularly in esthetic areas, in proximity of anatomical structures (ie, maxillary sinus, inferior alveolar nerve, and mental foramen), whenever the treatment plan requires delayed placement, and whenever patients ask to postpone implant insertion for various reasons. Socket debridement is advised before the use of a "regenerative material," and xenograft is considered the gold standard material to maintain ridge dimensions. Another indication is antibiotic therapy, which is recommended in the case of alveolar ridge preservation (amoxicillin 2 g 1 hour before the intervention and 1 g every 12 hours for 6 days). A membrane or autologous soft tissue should be used to seal the socket and protect the regenerative material, and the indicated reentry time (implant insertion) is 4 to 6 months. Conclusion: This Consensus Conference agreed that the adoption of alveolar ridge preservation can effectively prevent physiologic bone loss, especially in esthetic areas. It is recommended to cover the xenograft material with a membrane or autologous soft tissue, and antibiotic therapy is advisable