Synthesis of a tetraoxy-bis-nortaxadiene, en route to taxol, using a cascade radical cyclisation sequence

Concise syntheses of the substituted enynediones 28a, 33b and 36 starting from the cyclohexenealdehyde 18, corresponding to ring A in the taxanes, and the vinylstannane 24, are described. Treatment of 36 with Bu3SnH–AIBN did not lead to the oxy-substituted taxadiene 37 expected from a tandem radical macrocyclisation–radical transannulation sequence; instead, a mixture of unidentified products resulted. When the PMB ether 33b corresponding to the alcohol 36 was treated with Bu3SnH–AIBN under similar conditions, p-anisaldehyde was isolated, as a major by-product, but no evidence for the formation of a taxadiene could be observed. In contrast, the iododienynedione 41, i.e., deoxy 36, underwent a tandem radical macrocyclisation–transannulation sequence, when treated with Bu3SnH–AIBN, leading to the tetraoxy-bis-nortaxadiene 42 in 44% yield. Attempts to synthesise the alcohol 28b from the silyl ether 28a en route to the iodide 28c instead gave the substituted tetrahydrofuran 29 via an intramolecular oxy-Michael reaction.

Robust face recognition using posterior union model based neural networks

Face recognition with unknown, partial distortion and occlusion is a practical problem, and has a wide range of applications, including security and multimedia information retrieval. The authors present a new approach to face recognition subject to unknown, partial distortion and occlusion. The new approach is based on a probabilistic decision-based neural network, enhanced by a statistical method called the posterior union model (PUM). PUM is an approach for ignoring severely mismatched local features and focusing the recognition mainly on the reliable local features. It thereby improves the robustness while assuming no prior information about the corruption. We call the new approach the posterior union decision-based neural network (PUDBNN). The new PUDBNN model has been evaluated on three face image databases (XM2VTS, AT&T and AR) using testing images subjected to various types of simulated and realistic partial distortion and occlusion. The new system has been compared to other approaches and has demonstrated improved performance.

Radical 1,4-aryl transfer in arylcarboxamides leading to phthalimides, biaryls and enantiomerically enriched beta-arylethylamines

5-exo Cyclisation of vinyl-, aryl- and alkyl-radicals onto the aryl group of arylcarboxamides is followed by beta-scission of the resulting spirocyclohexadienyl radicals with ejection of a carbamoyl radical. The fate of this radical depends on the substrate but, in the cases studied, either 5-endo cyclisation or direct reduction follows to give phthalimides, biaryls or beta-arylethylamines.