Hiroaki Shitara

Preparation and properties of metallacyclobutanes of nickel and palladium

Abstract Bis(phosphine)-3,3-dimethylnickela- and palladacyclobutanes have been prepared by intramolecular C-H insertion reaction of the corresponding dineopentyl metal complexes. Nickelacyclobutane complexes decompose when heated thereby undergoing competitive carbon-carbon bond cleavage to give isobutene and ethylene, with reductive elimination affording 1,1-dimethylcyclopropane and skeletal isomeri-zation of the metallacyclic ring yielding 3-methyl-1-butene, whereas the palladium analog gave no significant amounts of CC bond cleavage products.Added phos-phine was seen to have an effect on CC bond scission of nickelacyclobutane complexes. Nickelacyclobutane complexes in solution are thought to be in equilibrium with olefin-coordinated nickel-carbene complex on the basis of available experimental evidence from hydrogenolysis, carbene-trap reactions with olefins and reaction with carbon monoxide

1H NMR study of chiral recognition of amines by chiral Kemp's acid diamide

Abstract Chiral recognition by homochiral Kemps acid diamide was studied by a 1 H NMR titration method. The diamide monoacid, prepared by amidation with enantiomerically pure ( S )-α-methylbenzylamine, gave a large chemical shift change for five amines studied and showed good enantioselectivity toward cis - N -benzyl-2-aminocyclohexanemethanol.

Solvent-Induced Reversed Stereoselectivity in Reciprocal Resolutions of Mandelic Acid and erythro-2-Amino-1,2-diphenylethanol

Solvent-induced chirality switching in reciprocal optical resolution between mandelic acid (1) and erythro-2-amino-1,2-diphenylethanol (2) has been demonstrated. The stereochemistry of the deposited salts was controlled by changing the crystallization solvent from 1-PrOH or 1-BuOH to 1,4-dioxane. It was revealed from (1)H NMR spectra, thermogravimetric analysis, and X-ray crystallography of the salts that an equimolar amount of the crystallization solvent was incorporated in each diastereomeric salt. On the basis of the crystal structures, it was found that both the hydrogen-bonding ability and the size of the solvent molecule played an important role. Differences in the formed hydrogen-bonding networks (columnar or sheetlike structure) and their packing manner were found to be crucial for the reversed stereoselectivity. Furthermore, pseudopolymorphic salt crystals that incorporated 1,4-dioxane were obtained during the enantioseparation of racemic 2, and their solid-state properties were examined by measurement of their IR spectra. This solvent-induced dual stereocontrol technique was successfully applied to the successive resolution process, eliminating the need to change the resolving agent for access to both enantiomers of 1 and 2.

Isolation of η2-(C,C) ketene complexes of nickel from the reactions of nickelacyclobutane complexes with carbon monoxide

The η2(C,C) ketene complex [Ni(CH2CO)(PPh3)2], a model complex for homogeneous CO reduction, was isolated by carbonylation of nickelacyclobutane complexes or by the reaction of [Ni(PPh3)4] with CH2Br2 in the presence of Zn followed by carbonylation.

Solvent-induced chirality control in the enantioseparation of 1-phenylethylamine via diastereomeric salt formation.

Solvent-induced chirality control in the enantioseparation of 1-phenylethylamine 1 by N-(p-toluenesulfonyl)-(S)-phenylalanine 2 via diastereomeric salt formation was studied. (S)-1·(S)-2 was preferentially crystallized as a less-soluble salt from aqueous alcohol, while (R)-1·(S)-2 salt was mainly obtained by addition of solvents with a six-membered ring such as dioxane, cyclohexane, tetrahydropyran, and cyclohexene to 2-propanol. Further investigations were carried out from the viewpoints of molecular structures, optical rotation measurement, and X-ray crystallographic analyses. Crystallographic analyses have revealed that incorporation of the six-membered ring solvent molecule in (R)-1·(S)-2 without hydrogen bonds changed the molecular conformation of (S)-2 to stabilize the salt, which changed the selectivity of 1 in the enantioseparation.

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemps acid diamides were synthesized and applied to chiral amine recognition using 1H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and π––π interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on 1H NMR data and computer simulation.

Economical synthesis of cyclic carbonates from carbon dioxide and halohydrins using K2CO3

A highly simple, economical, and selective synthesis of five-membered cyclic carbonates was achieved by the reaction of CO2 with 1,2-halohydrins in the presence of K2CO3. This method allows the efficient preparation of cyclic carbonates (72–95% yields for monosubstituted cyclic carbonates and 43% for 1,1- and 1,2-disubstituted cyclic carbonates) under mild reaction conditions, atmospheric pressure of CO2 at 30 °C, and not only in dry DMF, but also in commercial “anhydrous” DMF. The reaction mechanism was elucidated using the SEM and XRD data of the by-products, KHCO3 and KBr.