15N-, 1H-, and 13C-NMR chemical shifts and electronic properties of aromatic diamines and dianhydrides

We measured the ¹⁵N-, ¹H-, and ¹³C-NMR chemical shifts for a series of aromatic diamines and aromatic tetracarboxylic dianhydrides dissolved in DMSO-d₆, and discuss the relationships between these chemical shifts and the rate constants of acylation (k) as well as such electronic-property-related parameters such as ionization potential (IP), electronic affinity (EA), and the energy ε of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The ¹⁵N chemical shifts of the amino group of diamines (δ_N) depend monotonically on the logarithm of k (log k) and on IP. We inferred the reactivities of diamines whose acylation rates have not been measured from their δ_N, and we propose an arrangement of diamines in the order of their reactivity. The ¹H chemical shift of amino hydrogens (δ_H) and the ¹³C chemical shift of carbons bonded to nitrogen (δ_C) are roughly proportional to δ_N, but these shifts are not as closely correlated with log k and IP. Although the ¹³C chemical shifts of the carbonyl carbon of dianhydrides (δ_C,) varies much less than the δ_C and δ_N of diamines, δ_C, can be an index of acylation reactivity for dianhydrides because it is closely correlated with ε_LUMO. These facts indicate that the chemical shifts of diamines and dianhydrides are displaced according to their electron-donor and electron-acceptor properties, and that these chemical shifts can be used as indices of the electronic properties of monomers. Changes in reactivity caused by the introduction of trifluoromethyl groups into diamines and dianhydrides are inferred from the displacements of δ_N and δ_C © 1992 John Wiley & Sons, Inc.     

Encapsulation of Hb into unsaturated lipid vesicles and γ-ray polymerization

A carbonyl hemoglobin (HbCO) solution was stirred with a mixed powder of polymerizable 1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphocholine (DODPC), cholesterol and stearic acid (7/7/2 by mol). The mixture was extruded through polycarbonate membrane filters (final pore size = 0.2 μm Ø). The average diameter of the resulting vesicles was 203 ± 39 nm. The [Hb]/[Lipid] ratio (the weight ratio of Hb in vesicle to lipid) increased with the Hb concentration, and decreased with the NaCl concentration. A maximum [Hb]/[lipid] ratio was observed at pH 6.9, which was the same as the isoelectric point of Hb. The vesicles were stabilized by γ-irradiation (⁶⁰Co) because the bilayer lipids bound each other to yield polyphospholipids. Denaturation of Hb by γ-irradiation was not detected. These polyphospholipid vesicles encapsulating Hb were stable even against the freeze–thaw cycles and the freeze-drying procedure.     

Catalytic addition of C-H bonds to multiple bonds with the aid of ruthenium complexes

Ruthenium complexes, e.g., RuH2(CO)(PPh3)3, have been found to catalyze the direct addition of ortho carbon-hydrogen bonds of aromatic ketones to olefins and acetylenes with high efficiency and selectivity. The C-H/olefin coupling reaction is applicable to not only C-H bonds in aromatic ketones but also to those in a,b-enones and aro-matic esters. Catalytic addition of ortho carbon-hydrogen bonds of aromatic imines to olefins is found to be catalyzed by Ru3(CO)12.     

Trichloromethylative Olefin Lactonization by Photoredox Catalysis

A trichloromethylative olefin lactonization reaction using an iridium photoredox catalyst was developed. The reactions proceeded at room temperature for olefins with various substituents and substitution patterns, and a variety of lactones with a tetrasubstituted carbon and trichloromethyl group were obtained regio- and stereoselectively. The reaction mechanism was elucidated through isotope labeling experiments. The chemical properties of the lactones containing the trichloromethyl groups were investigated, and synthetic transformations of the product were realized.     

Synthesis,Structures, and Complexation with Phenolic Guests of Acridone-Incorporated Arylene–Ethynylene Macrocyclic Compounds

Acridone units were incorporated into the arylene–ethynylene structure as polar arene units. Cyclic trimers consisting of three acridone-2,7-diyl units and three 1,3-phenylene units were synthesized by Sonogashira couplings via stepwise or direct route. X-ray analysis revealed that the trimer had a nearly planar macrocyclic framework with a cavity surrounded by three carbonyl groups. In contrast, the corresponding tetramer had a nonplanar macrocyclic framework. ¹H NMR measurements showed that the trimer formed a 1 : 1 complex as a macrocyclic host with dihydric phenol guests, and the association constants were determined to be ca. 1.0×10³ L mol⁻¹ for hydroquinone or resorcinol guests in CDCl₃ at 298 K. The calculated structures of these complexes by the DFT method supported the presence of two sets of OH⋅⋅⋅O=C hydrogen bonds between the host and guest molecules. The spectroscopic data of the cyclic trimers and tetramers are compared with those of reference acridone compounds.     

Reaction of β-phenylthioalkyltitanium reagents with carbonyl compounds

β-Phenylthioalkyltitanium reagent prepared by the hydrotitanation of alkenyl sulfide using triethylsilane and titanium tetrachloride is found to react with aromatic aldehyde or α,β-unsaturated ketone to give the corresponding γ-hydroxyalkyl sulfide or δ-phenylthio ketone, respectively.     

Dramatic effects of boryl substituents on thermal ring-closing reaction of vinylallenes

The unidirectional thermal ring-closing reaction of cis-4-phenyl-5-borylpenta-1,2,4-triene giving 4-boryl-3-methylene-1-phenylcyclobutene proceeded significantly faster than that of the trans-isomer. The large rate difference between the cis- and trans-stereoisomers is ascribed to electronic participation of the vacant boron p orbital in the transition state SHOMO.