Highly Enantio- and Diastereoselective Synthesis of 2-Substituted 1-Bicyclo[3.1.0]hexanols

Useful intermediates in organic synthesis , optically active bicyclic cyclopropanols were difficult to prepare by existing methods. They can now be readily synthesized with high enantio- and diastereoselectivity from Oppolzer's N-acylcamphorsultams and [Ti(OiPr)₂(η²-propene)] [Eq. (a)]. R=alkyl, alkenyl, benzyl, alkoxyalkyl, alkylsiloxyalkyl.     

Macromolecular architecture of group 10 metal‐poly(yne)s: dendritic,hyperbranched, and helical macromolecules

Novel two‐ and three‐dimensional organometallic polymers of palladium and platinum have been prepared by choice of some acetylene linkages with characteristic structures. When o‐diethynylbenzene was used for a bridging ligand, a macrocyclic complex was selectively produced. Helical poly(yne) polymers were prepared from the reaction with chiral 1,1′‐bi(6‐ethynyl‐2‐naphthol). Platinum acetylide dendrimers, in which platinum atoms are linked by 1,3,5‐triethynylbenzene derivatives, have been prepared by a convergent method up to the third generation.     

Critical composition of ionic–nonionic mixed micelles for counterion condensation

In the mixed micelles of an ionic surfactant (sodium dodecyl sulfate) with a nonionic surfactant (N-decanoyl-N-methylglucamide, hexaoxyethylene glycol-mono-n-decylether, and hexaoxyethylene glycol-mono-n-dodecylether), the critical mole fraction, X_ic, of the ionic surfactant has been determined, below which the counterion is completely released from the micelles. The values of X_ic are 0.074, 0.11, and 0.11, for the respective nonionic surfactants. The valences, i.e., the aggregation numbers of the ionic surfactant, of the mixed micelles at X_ic are almost close to each other, around 6. At X_ic, the critical surface charge density (about 0.03 Cm^-2) for counterion condensation was tentatively calculated. In the present study, a differential conductivity method was applied.     

New convergent synthesis of 1alpha,25-dihydroxyvitamin D3 and its analogues by Suzuki-Miyaura coupling between A-ring and C,D-ring parts

A new convergent method for the synthesis of 1alpha,25-dihydroxyvitamin D(3) and its analogues has been developed that involves efficient preparation of the A-ring part 1a, (Z)-(3S,5R)-1-bromomethylene-3,5-bis(tert-butyldimethylsilyloxy)-2-methylenecyclohexane, starting from epichlorohydrin (4) and its Suzuki-Miyaura coupling reaction with the C,D-ring part 12. Thus, (R)-4 was converted to (3S,5R)-5-(tert-butyldimethylsilyloxy)-8-(trimethylsilyl)-oct-1-en-7-yn-3-ol (3a) through a ten-step reaction sequence in 49% overall yield. Compound 3a thus obtained was treated with a Ti(O-i-Pr)(4)/2 i-PrMgCl reagent and then with NBS to afford (Z)-(1S,2S,5R)-2-bromomethyl-3-[bromo(trimethylsilyl)methylene]-5-(tert-butyldimethylsilyloxy)cyclohexanol (10a) in 51% yield, from which 1a was obtained in 87% yield by sequential treatment with TBSCl/imidazole, DBU, and Cs(2)CO(3). The resulting A-ring intermediate 1a was reacted with alkenylboronate 12 in the presence of a PdCl(2)(dppf) catalyst to furnish 1alpha,25-dihydroxyvitamin D(3) in 82% yield after protodesilylation. Similarly, all of the other three possible stereoisomers of A-ring parts 1b, 1c, and 1d were prepared, from which 1-epi-, 3-epi-, and 1,3-di-epi-1alpha,25-dihydroxyvitamin D(3) were synthesized by coupling with 12 in excellent yield, respectively. Starting from 1a and 1c, des-C,D-1alpha,25-dihydroxyvitamin D(3) analogues, retiferol 13 and its 3-epi derivative, were also prepared, respectively.     

Structural transition of glucagon in the concentrated solution observed by electrophoretic and spectroscopic techniques

Glucagon, a polypeptide hormone consisting of 29 amino acid residues, tends to form gel-like fibrillar aggregates, and the glucagon fibril, as well as other pathologically related fibrils including prion, amylin, and beta-amyloid, have been found to be cytotoxic through the activation of apoptotic signaling pathways. To understand the aggregation properties of glucagon fibril, we have characterized and compared the physicochemical properties of glucagon, secretin, a member of the glucagon superfamily, and amylin using analytical techniques including capillary electrophoresis (CE), circular dichroism (CD), FT-IR, FT-Raman, transmission electron microscopy (TEM), and beta-sheet-imaging probe. Aging treatment of glucagon resulted in the formation of fibrillar aggregates in time- and concentration-dependent manner, and FT-IR and FT-Raman analyses showed the spectral shift of amide I band, suggesting the conformational changes from alpha-helix to beta-sheet structure. Interestingly, secretin, having high sequential and secondary structural homology with glucagon, did not generate the fibrillar aggregates at the conditions tested. In addition, we evaluated the association state of glucagon at various pHs raging from pH 2.0 to 3.5 using CE. Based on the CE data, the rate constants of glucagon aggregation were calculated to be 0.002 +/- 0.004/h and 0.080 +/- 0.011/h for aging at pH 2.0 and 3.5, respectively, suggesting the pH dependence of self-association. CE showed the potential to separate and detect the glucagon aggregates and intermediates during aging process.     

Reactions of nitrogen monoxide on cobalt cluster ions: reaction enhancement by introduction of hydrogen

Absolute cross sections for NO chemisorption, NO decomposition, and cluster dissociation in the collision of a nitrogen monoxide molecule, NO, with cluster ions Con+ and ConH+ (n=2-5) were measured as a function of the cluster size, n, in a beam-gas geometry in a tandem mass spectrometer. Size dependency of the cross sections and the change of the cross sections by introduction of H to Con+ (effect of H-introduction) are explained by a statistical model based on the RRK theory, with the aid of the energetics obtained by a DFT calculation. It was found that the reactions are governed by the energetics rather than dynamics. For instance, Co3+ does not react appreciably with NO because the reactions are endothermic, while Co3H+ does because the reaction becomes exothermic by the H-introduction.     

A convenient method for the preparation of 3-trimethylsilyl-2,5-dihydrofurans and their conversion to furans

Hydromagnesiation of 3-trimethylsilyl-2-propyn-1-o1 (1) followed by reaction with aldehydes or ketones affords (E)-3-trimethylsilyl-2-alken-1,4-diols (2), which can be readily dehydrated to 3-trimethylsilyl-2,5-dihydrofurans (3) by treatment with BF₃OEt₂. The compounds (3) are converted to furans (5) by epoxidation and subsequent treatment with H₂SO₄.