Dimethylzinc-mediated addition of alkenylzirconocenes to alpha-keto and alpha-imino esters

[reaction: see text] Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.     

CHEMISTRY OF SINGLET OXYGEN—XXVI. PHOTOOXYGENATION OF PHENOLSy†

Abstract— The aerobic dye-sensitized photooxygenation of monohydric phenols proceeds by way of singlet oxygen under the conditions studied. Various phenols give different proportions of reaction with and quenching of singlet oxygen. Para-substituted 2,6-di-t-butylphenols show a linear correlation between the log of the total rate of singlet oxygen removal and their halfwave oxidation potentials; the same correlation is given for certain phenol methyl ethers. A Hammett plot using s?⁺ gives ρ - 1.72 ± 0.12, consistent with development of some charge in the quenching step. Reaction of photo-chemically generated singlet oxygen with 2,4,6-triphenylphenol gives 2,4,6-triphenylphenoxy radical as an intermediate in singlet oxygen quenching, although no overall reaction occurs. Kinetic analysis indicates that the radical is derived exclusively from the interaction of 2,4,6-triphenylphenol with singlet oxygen. A charge-transfer mechanism for quenching of singlet oxygen by phenols is proposed.     

Field ionization mass spectrometry—IV. Isotopically labeled heptanals

The field ionization (FI) mass spectra of n-heptanal and a series of deuterium labeled analogs have been studied, with the objectives of initiating systematic investigations of reaction mechanisms of FI produced ions and to permit comprison with those found for other ionization processes. It is now recognized that FI ions have: (a) lower average internal energies and (b) shorter residence times than similar ions generated by electron-impact (EI), and the possibility exists of H/D-randomization occuring in ions formed by desorption from the emitter, by unimolecular decomposition close to the emitter and by either ‘fast’ or ‘slow’ metastable decompositions. In this study only the peak shifts of normal ions could be utilized; accurate mass measurements of all major ions revealed elemental compositions similar to EI. A site-specific McLafferty rearrangement gave the base peak at m/e 44 ([C₂H₄O]^+.), although the apparently complementary ion at m/e 70 ([C₅H₁₀]^+.) arose in a less specific process. Ions at m/e 43 ([C₃H₇]⁺) and 71 ([C₅H₁₁]⁺ 80%; [C₄H₇O]⁺ 20%) were apparantly generated without significant H/D-scrambling. Of special interest was the observation of the rearrangement ion at m/e 86 ([C₅H₁₀O]^+.) caused by loss of C-2 and C-3 as C₂H₄, as found for EI. It is concluded that at least in this system, decomposing molecular ions formed: (a) in the gas phase extremely close to the emitter and/or (b) on the emitter surface, have lifetimes sufficiently short to preclude complete H/D randomization. The results also provide evidence for common fragmentation mechanisms for heptanal molecular ions at both the low end and the high end of the energy distribution.     

A CNDO/INDO crystal orbital model for transition metal polymers of the 3d series—basis equations

The crystal orbital formalism in the tight-binding approximation is combined with a recently developed CNDO/INDO model for transition metal species of the 3d series in order to allow band structure calculations on the Hartree-Fock (HF) SCF level for one-dimensional (1D) chains with organometallic unit cells. The band structure approach based on the CNDO and INDO approximation can be used for any atom combination up to bromine under the inclusion of the 3d series. The matrix elements for the tight-binding Hamiltonian are derived for an improved CNDO and INDO framework. The total energy of the 1D chain is partitioned into one-center contributions and into two-center increments of the intracell and intercell type. Semiempirical band structure calculations on simple model systems are compared with available ab initio data of high quality.     

Isomerisation in the chemistry of platinacyclobutane complexes

The platinacyclobutane complexes PtCl₂L₂(C₃H₅Me)], L  pyridine, CD₃CN, or tetrahydrofuran, exist as mixtures of isomers containing P$\text{tCH}{}_2\text{CHMeC}$H₂ or P$\text{tCHMeCH}{}_2\text{CH}{}_2$ groups in rapid equilibrium. Decomposition occurs in some cases to give [PtCl₂L(CH₃CH₂CHCH₂)]. Stereospecific skeletal isomerisation also occurs in metallocyclobutanes containing the groups P$\text{tCHRCHRC}$H₂  P$\text{tCHRCH}{}_2\text{C}$HR, when R  aryl further decomposition gives ν-allylplatinum complexes.     

Equilibria in complexes of N-heterocyclic molecules,part XII. The reaction of hydroxide and alkoxide Ions with platinum(II) complexes of 5-nitro-1,10-phenanthroline and 2,2′-bipyridyl

Summary Bis-(5-nitro-1,10-phenanthroline)platinum(II) dichloride and diperchlorate have been prepared. The reaction between the parent cation and hydroxide ion has been studied using 1 FI n.m.r. spectroscopy and found to involve attack at the ligand. The bis-(2,2-bipyridyl)platinum(II) ion has been shown to be highly reactive towards methoxide ion. The dissociation of a 2,2-bipyridyl ligand is preceded by attack at the ligand.Part XI: R. D. Gillard, t.. A. P. Kane-Maguire and P. A. Williams,Transition Met. Chem., 2, 47 (1977).On leave from the University of Baghdad, Iraq.     

Kinetic studies in mass spectrometry—IV. The [M — Cl] reaction in substituted chlorobenzenes and the question of molecular ion isomerization.

The [M]⁺˙ → [M ? Cl]⁺ reaction in a series of m- and p-X substituted chlorobenzenes has been studied, utilizing a simple kinetic approach, comparison of metastable ion relative abundances, and by measurement of ionization and appearance potentials. All evidence obtained is consistent with rearrangement prior to cleavage in the molecular ions, in which substituent position becomes effectively randomized. These findings are related to known hydrogen randomization reactions occurring in either the molecular ion or [M ? Cl] ion of chlorobenzenes. Mechanisms involving carbon scrambling via such species as ionized benzvalenes or prismanes, or ring-opening to isomeric acyclic molecular ions in which hydrogen randomization might occur can be entertained, but mechanisms involving simple hydrogen shifts in the intact benzene ring appear less likely.     

Solution structure of a beta-peptide ligand for hDM2

We recently reported a beta-peptide foldamer, beta53-1, that folds into a 14-helix in aqueous solution, binds the oncoprotein hDM2 with submicromolar affinity, and potently inhibits the interaction of hDM2 with a peptide derived from the activation domain of p53 (p53AD). Here, we present the solution structure of beta53-1 in methanol. Details of the structure illustrate fundamental and novel elements of beta-peptide folding and recognition. These elements include the detailed arrangement of a complex, 14-helix-stabilizing salt bridge on one helical face, and a unique "wedge into cleft" packing interaction along a second. The structure also reveals how a subtle distortion in the beta53-1 14-helix geometry alters the presentation of its recognition epitope, rendering it particularly well suited for alpha-helix mimicry. The solution structure of beta53-1 demonstrates that well folded beta-peptide oligomers can effectively present an extended, highly variable surface that could be used as a general platform for targeting critical protein-protein interfaces.     

Sizes and interfacial free energies of crystallites formed from fractionated linear polyethylene

Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 10³?5.7 × 10⁵. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight.     

Homoatomic P --> P coordination: a versatile synthetic approach to polyphosphorus dications

Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems.