Mass spectral fragmentations of 6-aryl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-Oxides

The mass spectral fragmentation of 4-, 5-, and 4,8-disubstituted derivatives of 6-aryl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides is reported.     

An effective method to use ionic liquids as reaction media for asymmetric reduction by Geotrichum candidum

An effective method was developed to use an enzyme in ionic liquids; the asymmetric reduction of ketones by Geotrichum candidum in ionic liquids proceeded smoothly with excellent enantioselectivity when the cell was immobilized on water-absorbing polymer containing water, while the reaction without the polymer did not proceed.     

Potential energy surfaces and nonadiabatic transitions in the asymptotic regions of ICN photodissociation to study the interference effects in the F1 and F2 spin-rotation levels of the CN products

One of the most spectacular yet unsolved problems for the ICN -band photodissociation is the non-statistical spin-rotation F₁ = N + 1/2 and F₂ = N − 1/2 populations for each rotation level N of the CN fragment. The F₁/F₂ population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (²P_3/2) and I (²P_1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F₁ and F₂ levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N . We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F₁ and F₂ level populations observed by Zare's group and Hall's group, respectively. © 2018 Wiley Periodicals, Inc.     

Synthesis of 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides

Four 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides were synthesized by the reaction of the corresponding N,N-bis(2-hydroxyethyl)aniline with thionyl chloride in the presence of triethylamine.     

Lannotinidines A-G, new alkaloids from two species of Lycopodium

Seven new Lycopodium alkaloids, lannotinidines A-G (1-7), have been isolated from the club moss Lycopodium annotinum and L. annotinum var. acrifolium. Stereochemistry of 1-7 was elucidated by combination of NOESY correlations and chemical transformation. Lannotinidines B-E (2-5) elevated NGF mRNA expression.     

Synchrotron X-ray structures of cellulose I<Subscript>β</Subscript> and regenerated cellulose II at ambient temperature and 100 K

Synchrotron X-ray data have been collected to 1.4 Å resolution at the NE-CAT beam-line at the Advanced Photon Source from fibers of cellulose I_β and regenerated cellulose II (Fortisan) at ambient temperature and at 100 K in order to understand the effects of low temperature on cellulose more thoroughly. Crystal structures have been determined at each temperature. The unit cell of regenerated cellulose II contracted, with decreasing temperature, by 0.25%, 0.22% and 0.1% along the a, b, and c axes, respectively, whereas that of cellulose I_β contracted only in the direction of the a axis, by 0.9%. The value of 4.6×10^?5 K^?1 for the thermal expansion coefficient of cellulose I_β in the a axis direction can be explained by simple harmonic molecular oscillations and the lack of hydrogen-bonding in this direction. The molecular conformations of each allomorph are essential unchanged by cooling to 100 K. The room temperature crystal structure of regenerated cellulose II is essentially identical to the crystal structure of mercerized cellulose II.     

A highly cis-selective synthesis of 2-ethynylaziridines by intramolecular amination of chiral bromoallenes: improvement of stereoselectivity based on the computational investigation

The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by B3LYP density functional calculations together with the 6-31+G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.     

Dynamic coordination polymers with 4,4'-oxybis(benzoate): reversible transformations of nano- and nonporous coordination frameworks responding to present solvents

Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1.     

Enantiodifferentiating photoaddition of alcohols to 1,1-diphenylpropene in supercritical carbon dioxide: sudden jump of optical yield at the critical density

In the enantiodifferentiating photoaddition of ROH (R = Me, Et, i-Pr) to 1,1-diphenylpropene sensitized by fructosyl 1,4-naphthalenedicarboxylate in supercritical carbon dioxide, the enantiomeric excess of photoadduct increased with increasing bulkiness of the alcohol at all pressures used, with an accompanying sudden jump at the critical density, for which the enhanced clustering of alcohol, particularly in the subcritical pressure region, was revealed to be responsible from the fluorescence spectral examinations.