Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage

N-Nitrosamines can be considered as potential nitric oxide (NO)/nitrosonium ion (NO(+)) donors. However, the relation of the structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO(+) remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso group in the solid state, we postulate that N-NO bond cleavage of N-nitrosamines is enhanced by a reduction of the resonance in the N-NO group. Computational studies suggest that these structural features of the N-nitrosamines of 7-azabicyclo[2.2.1]heptane are derived from angle strain imposed on the CNC angles.     

On the pauling electronegativity scales—II

From the analysis of the electrostatic potential near the core-valence boundary in an atom, it is shown that the Pauling electronegativity scale χ_p is approximately given by the formula,

where N_v is the valence electron number and f(n) is some function of the periodic number in the periodic table. It is also shown in detail that the Pauling electronegativity scale is closely related to the Wang-Parr electronegativity scale which is determined as the negative of the chemical potential in density functional theory. Correlation between the Pauling and Mulliken electronegativities is briefly discussed.     

On the Pauling electronegativity scales—I

It is shown that the Pauling electronegativity scale χ is closely related to the electrostatic potential near the physical meaningful boundary between the core and valence regions in an atom, and is well reproduced by the relationship:

where N_ν is the valence electron number and the factor f(n) is empirically given by

n being the periodic number.     

Generation of functionalized asymmetric benzynes with TMP-zincates. Effects of ligands on selectivity and reactivity of zincates

We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various meta-substituted bromobenzenes with Me2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particularly those electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with tBu2Zn(TMP)Li, followed by electrophilic trapping (with I2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds.8 The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions with Me3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be of value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions.     

A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′-diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′-dihydroxyketone.     

Rationale for the acidity of Meldrum's acid. Consistent relation of C-H acidities to the properties of localized reactive orbital

Detailed investigation on the origin of the acidity of the alpha-protons of a set of the carbonyl molecules was carried out on the basis of properties of the localized molecular orbital. An anomalously high acidity of Meldrum's acid, as compared with those of dimedone and dimethyl malonate, is one of the well-known but unresolved issues. The well-localized sigma orbitals of the C-H bonds at the alpha-position of the carbonyl groups can be obtained with the reactive hybrid orbital (RHO) theory. We found that the energy levels of the unoccupied RHOs of the C-H moiety of Meldrum's acid and other carbonyl compounds showed a good linear correlation with the experimental deprotonation energies. This is probably because the deprotonation reaction to form the proposed naked anions in a polar solvent is a highly endothermic process, in which the thermodynamic energy differences between the neutral molecules and the corresponding anions approximately coincide with the activation energies. We also investigated the effect of the conformational change upon deprotonation on the electron-accepting energy level of the relevant C-H bonds of cyclic/acyclic and monocarbonyl/dicarbonyl compounds. A conformational change occurs in the cases of cyclic six-membered compounds, but its influence on the reactivity of the C-H bond is small. The acidity of dicarbonyl compounds, including Meldrum's acid, showed a good correlation with the deviations from the perpendicular position of the dihedral angles of the relevant C-H bond with respect to the adjacent carbonyl C=O bond. This angle parameter can be related to the magnitude of the in-phase orbital interaction between the sigma(CH) and pi(C)(=)(O) orbitals, which facilitate electron acceptance. These results indicated that the acidity of the alpha-proton of carbonyl compounds can be represented in terms of the electron-accepting orbital levels of the unoccupied RHO of the C-H moiety. All the linear relationships found in the present work strongly suggested that the acidity of Meldrum's acid, which is conventionally regarded as an anomaly, is consistent with those of the other carbonyl compounds.     

Charge-order pattern of the low-temperature phase from a monoclinic single domain of NaV2O5 uniquely determined by resonant x-ray scattering

The present resonant x-ray scattering has been performed on a monoclinically split single domain of NaV(2)O(5). The observation of a critically enhanced contrast between V(4+) and V(5+) ions has led us to the unequivocal conclusion of the charge-order pattern of the low-temperature phase of NaV(2)O(5) below T(c) = 35 K. In spite of the possible four types of configuration of the zigzag-type charge-order patterns in the ab plane (A,A',B and B'), the stacking sequence along the c axis is determined as the AAA'A' type by comparison with model calculations.     

Cp2TiCl2-catalyzed regio- and chemoselective one-step synthesis of gamma-substituted allylsilanes from terminal alkenes using dianion-type zincate (SiSiNOL-Zn-ate)

A regio-/chemoselective silylation reaction of various functionalized terminal alkenes in the presence of titanocene dichloride, based on a newly designed dianion-type zincate, was developed. The present silylation of terminal alkenes is a powerful tool for the one-pot generation of regiocontrolled functionalized allysilanes, which are available for various transformation reactions, such as hydroxyalkylation, epoxidation, and hydroboration.     

Sarason’s interpolation theorem for analytic crossed products

Saito (Math. Proc. Camb. Phil. Soc., 117, 11–20, 1995) proved Sarason’s interpolation theorem for an analytic crossed product determined by a finite von Neumann algebra. We extend this result without the assumption that the von Neumann algebra is finite.     

Certain invariant subspace structure of

In this note, we study certain structure of an invariant subspace of . Considering the largest -invariant (resp. -invariant) subspace in the wandering subspace of with respect to the shift operator , we give an alternative characterization of Beurling-type invariant subspaces. Furthermore, we consider a certain class of invariant subspaces.