2,3,7‐Triazabicyclo[3.3.0]octenes Prepared by Tandem Cascade Reaction of Allyl Azides and Olefinic Dipolarophiles

Tandem cascade reactions of allylazides and olefinic dipolarophiles to give cis‐fused 2,3,7‐triazabicyclo [3.3.0]octenes ( 5, 6 or 7 ) are reported. Therein, an intermolecular dipolar cycloaddition of azide and alkene gave a triazoline which was followed by isomerization of the triazoline to a diazoester ( 4 ) and then an intramolecular dipolar cycloaddition from the diazo functional group and the double bond in 4 to give 5 . Compound 5 may further more undergo a Michael addition to give 7‐substituted‐ 2,3,7‐ triazabicyclo [3.3.0]oct‐2‐ene ( 6 ) or a tautomerization to give 2,3,7‐triazabicyclo[3.3.0]oct‐3‐ene ( 7 ). The reaction may be manipulated to stop at a particular stage by adopting a suit able solvent or an appropriate temperature.     

Selected ion flow tube mass spectrometry analyses of stable isotopes in water: Isotopic composition of H3O+ and H3O+(H2O)3 ions in exchange reactions with water vapor

A new method has been developed for the determination of the isotope abundance ratios of deuterium, D, and oxygen-18, 18O, in water vapor (and water) using selected ion flow tube mass spectrometry (SIFT-MS). H3O+ ions are injected into the helium carrier gas where they associate with the H2O and HDO molecules in a sample of water introduced into the carrier gas. The D and 18O contents of the product cluster ions H8DO4+ and H9(18)OO3+ at m/e = 74 and 75, respectively, are determined by reference to the majority cluster ion H9O4+ at m/e = 73. Allowance is made for the contribution of the H8(17)OO3+ ions to the m/z = 74 ions. Absolute isotopic ratios are measured within seconds without the need for precalibration of the SIFT-MS instrument, currently to an accuracy of better than 2%.     

The Aldol Reaction of Allenolates with Aldehydes in the Presence of Magnesium Diiodide (MgI2) as Catalyst

Stereoselective synthesis of (Z)‐α‐(hydroxyalkyl)‐β‐iodoacrylates (=(2Z)‐2‐(hydroxyalkyl)‐3‐iodoprop‐2‐enoates) was achieved in a one‐pot coupling reaction from methyl prop‐2‐ynoate, Me₃SiI, and an alkanal under mild conditions with MgI₂ as catalyst (→ 1 – 9 ; see Table and Scheme 1). Baylis‐Hillman β‐iodo adducts were generated in excellent yields with high (Z)‐selectivity. The conversion of methyl prop‐2‐ynoate to an active methyl 3‐iodo‐1‐[(trimethylsilyl)oxy]allenolate intermediate in situ followed by carbonyl addition is proposed as the reaction sequence (Schemes 1 and 2).     

Synthesis of titanium(IV) guanidinate complexes and the formation of titanium carbonitride via low-pressure chemical vapor deposition

The mono(guanidinato) complex [Ti(NMe2)2Cl{i-PrNC[N(SiMe3)2]N-i-Pr}] (1) was prepared by reaction of [Ti(NMe2)2Cl2] with 1 or 2 equiv of the lithium guanidinate salt [Li{i-PrNC[N(SiMe3)2]N-i-Pr}]. Compound 1 has been characterized by X-ray crystallography. Treatment of TiCl4 with 2 equiv of [Li{i-PrNC[N(SiMe3)2]N-i-Pr}] resulted in the formation of dark red crystals. X-ray crystallography showed that these crystals consist of a 70:30 mixture of two bis(guanidinato) complexes, namely, [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC(N=CMe2)N-i-Pr}] (2) and [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC[N(H)-i-Pr]N-i-Pr}] (3). Both compounds 2 and 3 possess a transformed guanidinate ligand. Low-pressure chemical vapor deposition of either compound 1 or [TiCl2{i-PrNC(NMe2)N-i-Pr}] (4) at 600 degrees C results in thin films of titanium carbonitride.     

Tasumatrols P – T,Five New Taxoids from Taxus sumatrana

The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells.     

Synthesis of octahydroquinolines through the Lewis acid catalyzed reaction of vinyl allenes and imines

The reaction of vinyl allenes with imines under Lewis acid catalysis has been explored. Vinyl allenes in which the allenic portion of the molecule is tri- or tetrasubstituted gave octahydroquinoline derivatives as single isomers together with a minor compound formed by an ene reaction of the imine with the allene. Compounds in which the allene is 1,3-disubstituted do not react under the conditions assayed.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

The design, synthesis and evaluation of high affinity macrocyclic carbohydrate inhibitors

Carbohydrate-protein interactions have been investigated for a model system of a monoclonal antibody, SYA/J6, which binds a trisaccharide epitope of the O-polysaccharide of the Shigella flexneri variant Y lipopolysaccharide. The thermodynamics of binding for the methyl glycoside of the native trisaccharide epitope, Rha-Rha-GlcNAc () to SYA/J6 over a range of temperatures exhibits strong, linear enthalpy-entropy compensation and a negative heat capacity change (DeltaC(p)=-152 cal mol(-1) degree(-1)). At 293 K the free energy of association is the sum of favourable enthalpy and entropy contributions (DeltaH=-3.9 kcal mol(-1) and -TDeltaS=-2.9 kcal mol(-1)). Crystal structures for SYA/J6 Fab detailed the position of the native trisaccharide epitope, Rha-Rha-GlcNAc, and facilitated a strategy to design a tighter binding, low molecular weight ligand. This involved pre-organization of the native trisaccharide in its bound conformation by addition of intramolecular constraints (a beta-alanyl or glycinyl tether). ELISA measurements indicated that the glycinyl tethered trisaccharide was not an optimal candidate for further analysis, while microcalorimetry provided data showing that the beta-alanyl tethered trisaccharide displayed a 15-fold increase in affinity for SYA/J6. Tethering resulted in a favourable entropic contribution to binding, relative to the native trisaccharide (-TDeltaDeltaS=-1.2 kcal mol(-1)). Potential energy and dynamics calculations using the AMBER Plus force fields indicated that trisaccharide adopted a rigid conformation similar to that of the bound conformation of the native trisaccharide epitope. While this strategy resulted in modest free energy gains by minimizing losses due to conformational entropy, thermodynamic data are consistent with significant contributions from solvent reorganization.     

Mathematical Correction for Polyatomic Isobaric Spectral Interferences in Determination of Lanthanides by Inductively Coupled Plasma Mass Spectrometry

The determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS) is complicated by several spectral overlaps from M⁺, MO⁺ or MOH⁺ ions formed in the ICP. Especially, it is essential to avoid the spectral interferences from lighter lanthanide and Ba polyatomic ions on middle or heavier lanthanides. To tackle this problem, we have developed a mathematical correction method, which reduces all the spectral overlaps from oxide species of Pr, Nd, Ce and Sm over Gd, Tb, Dy and Ho, and Gd, Tb over Yb and Lu. It can also successfully correct the oxide and hydroxide interference of Ba over Eu. The effectiveness of the proposed the mathematical correction scheme is demonstrated for the USGS Standard Rock samples AGV‐1 and G‐2. The results show that the experimental data obtained by applying the mathematical correction scheme for lanthanides is in good agreement with the reported values, using pneumatic and ultrasonic nebulisation methods, for their ICP‐MS analysis.     

Enantioselective separation on a naturally chiral surface

Kinked-stepped, high Miller index surfaces of metal crystals are chiral and, therefore, exhibit enantiospecific properties. Previous temperature-programmed desorption (TPD) spectra have shown that the desorption energies of R-3-methylcyclohexanone (R-3-MCHO) on the chiral Cu(643)(R) and Cu(643)(S) surfaces are enantiospecific (J. Am. Chem. Soc. 2002, 124, 2384). Here, a comparison of the TPD spectra from Cu(111), Cu(221), Cu(533), Cu(653)(R&S), and Cu(643)(R&S) surfaces reveals that the enantiospecific desorption occurs from the chiral kink sites on the Cu(643) surfaces. Titration of the chiral kink sites with I atoms confirms this assignment of desorption features in the TPD spectra. Finally, the enantiospecific difference in the desorption energies of R- and S-3-MCHO has been used as the basis for demonstration of an enantioselective, kinetic separation of racemic 3-MCHO into its purified components during adsorption and desorption on the Cu(643)(R&S) surfaces.