双核银络合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成与结构

二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。     

Ab Initio Study of Prednisolone, 6α-Fluoroprednisolone, 9α-Fluoroprednisolone,and 6α,9α-Difluoroprednisolone

A theoretical study of prednisolone, 6-fluoroprednisolone, 9-fluoroprednisolone, and 6,9-difluoroprednisolone has been performed at the ab initio HF/6-31G, MP2/6-31G, and B3LYP/6-31G levels. Structural information and the electronic features of prednisolone and its derivatives and the synergistic effect of 6,9-difluoroprednisolone was examined. Contrary to the AM1 and MNDO results, we found 9-fluoroprednisolone is more stable than the 6-fluoroprednisolone. The increased corticosteroid activity of the 6,9-difluoroprednisolone is most likely due to electronic effects, mainly related to the receptor binding.     

Isoochotensine,a New Spirobenzyusoquinoline Alkaloid from: Corydalis Ochotensis Turcz

Separation of the phenolic fraction of Corydalis ochotensis afforded a new spirobenzylisoquinoline alkaloid, isoochotensine ( 1 ) and three known alkaloids, ochotensine ( 3 ), cheilanthifoline ( 7 ), and lienkonine ( 9 ) as their acetyl derivatives together with a known nonphenolic alkaloid, ochotensimine ( 5 ). Their structures were elucidated by the spectral data.     

Syntheses of seven-membered rings: ruthenium-catalyzed intramolecular [5+2] cycloadditions

The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates.     

Cationic polymerization with boron halides. V. Synthesis of poly(isobutylene-b-styrene) and poly(styrene-b-isobutylene)

Block copolymers of isobutylene and styrene, PIB-b-PSt and PSt-b-PIB, have been prepared by a two-step synthesis involving (1) preparation of terminally chlorinated (telechelic) polyisobutylene or polystyrene “prepolymers” by using the H₂O/BCl₃ initiator system and (2) blocking from these telechelic prepolymers a second polymer segment by using an alkyaluminum, e.g., Et₂AlCl coinitiator. The telechelic polyisobutylene and polystyrene contain tertiary and benzylic chlorine termini, respectively. Block copolymer characterization included detailed selective solvent extraction procedures, coupled with GPC determinations, PMR, solubility, and intrinsic viscosity studies. The synthesis of PIB-b-PSt and PSt-b-PIB provides direct chemical evidence for the presence and position of active chlorine termini in BCl₃-coinitiated olefin polymerizations.