Allylic substitution with sp(2)-carbon reagents (aryl and alkenyl anions) was realized by using allylic picolinates and copper reagents derived from RMgBr and CuBr x Me(2)S to afford anti S(N)2' products regio- and stereoselectively. Steric and electronic factors in the reagents and the size of the methylene substituents around the allylic moiety marginally affected the selectivity. The reaction system was compatible with alkyl reagents as well. Furthermore, the substitution was applied to construction of a quaternary center and synthesis of (-)-sesquichamaenol. Electron-withdrawing nature of the pyridyl group and chelation of the C(=O)-C(5)H(4)N to MgBr(2) generated in situ were found to be responsible for the high efficiency of the substitution.
The picolinoxy group was found to be an extremely powerful leaving group for allylic substitution with aryl nucleophiles derived from ArMgBr and CuBr*Me2S. The substitution proceeds with anti SN2' pathway and with high chirality transfer. The electron-withdrawing effect of the pyridyl group and chelation to MgBr2 are likely the origin of success. Results suggesting these effects were obtained.
A simple formula which describes multi-scattered neutron flux in a spherical cavity was derived based on the albedo concept. The formura treats a neutron source which has an arbitrary energy-angle distribution and is placed a t any point in the cavity. T h e derived formula was applied to the estimation of neutron fluxes in two cavities, i.e. a spherical concrete cell with a 14-MeV neutron source a t the center and the "YAYOI" reactor cavity with a pencil beam of reactor neutrons. The results of the analytical formula agreed very well with the reference data in the both problems. It was concluded that the formula is applicable to estimate the neutron fluxes in a spherical cell except for special cases that tangential source neutrons are incident to the cavity wall.
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