Stable meso–meso‐Linked 2NH‐Corrole Radical Dimers as a Key Intermediate to Corrole Tape

While oxidation of 5,5′,15,15′‐tetramesityl‐10‐10′‐linked 3NH‐corrole dimer with DDQ gave the corresponding triply linked 2NH‐corrole tape, the use of an equimolar amount of p‐chloranil as a milder oxidant resulted in the formation of a 10‐10′‐linked neutral 2NH‐corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10‐10′‐linked bis‐pyridine‐coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.     

Polyether-bridged bis(tert-butyl nitroxide) paramagnetic hosts showing receptor ability to calcium(II) and barium(II) ions

The title compounds, Ph2bNO and Ph3bNO, were designed as a biradical paramagnetic host, and their chelation ability was confirmed by inclusion of a size-matched alkaline-earth metal ion. The crystal structures of [Ca(hfac)₂(Ph2bNO)] and [Ba(hfac)₂(Ph3bNO)] were determined, where Hhfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dione. The solution electron paramagnetic resonance spectra showed switching behavior. Five lines were found for Ph3bNO and charecterized as the hyperfine splitting due to the two nitrogen atoms. After addition of barium(II) ion, the spectrum turned to be three lines. Removal of the barium ion recovered the five line pattern. The present system can be regarded as a reversible magnetic-coupling switch by means of a supramolecular technique.     

Chemical and genetic diversity of Ligularia virgaurea collected in northern Sichuan and adjacent areas of China. Isolation of 13 new compounds

Root chemicals and DNA sequences were analyzed for Ligularia virgaurea collected in the northern Sichuan Province and adjacent areas of China. Thirty-eight samples were found to contain five chemotypes, two known and three new ones. From samples of the new chemotypes, 13 new compounds were isolated, including 3 sesquiterpene dimers and some rearranged eremophilanes. The DNA sequences suggested that the chemotype differentiation had a genetic origin.     

Diisobutylaluminum hydride-promoted cyclization of silylated 1,3-dien-5-ynes: Application to total synthesis of a 20-norabietane derivative

The diisobutylaluminum hydride (DIBAL-H)-promoted benzocyclization, recently developed by this group, was adopted for the synthesis of a natural product containing a 9,10-dihydrophenanthrene skeleton to demonstrate its synthetic utility. One of the extracts from the roots of Salvia hydrangea DC. ex Bentham (Lamiaceae), a 20-norabietane derivative, was selected as the target molecule. The key step forming the 9,10-dihydrophenanthrene skeleton was achieved by the DIBAL-H-promoted cyclization of a silylated 1,3-dien-5-yne easily accessible from a substituted α-tetralone.     

Enantioselective Protonation of Cyclic Carbonyl Ylides by Chiral Lewis Acid Assisted Alcohols

Chiral Lewis acid-catalyzed asymmetric alcohol addition reactions to cyclic carbonyl ylides generated from N-(α-diazocarbonyl)-2-oxazolidinones featuring a dual catalytic system are reported. Construction of a chiral quaternary heteroatom-substituted carbon center was accomplished in which the unique heterobicycles were obtained in good yields with high stereoselection. The alcohol adducts were successfully converted to optically active oxazolidine-2,4-diones by hydrolysis. Mechanistic studies by DFT calculations revealed that alcohols could be activated by Lewis acids, enabling enantioselective protonation of the carbonyl ylides.     

Asymmetric synthesis of bicyclo[n.1.0]alkanes by the enantioselective 1,3-CH insertion reaction of chiral magnesium carbenoids

Treatment of enantiomerically pure 1-chlorovinyl p-tolyl sulfoxides, derived from cyclic ketones and (R)-chloromethyl p-tolyl sulfoxide, with the lithium enolate of tert-butyl carboxylates gave adducts in quantitative yields as single diastereomers. The adducts were treated with i-PrMgCl in toluene to afford optically active bicyclo[n.1.0]alkanes bearing a tert-butyl carboxylate moiety in up to 99% enantiomeric excess through the enantioselective 1,3-CH insertion reaction of the generated chiral magnesium carbenoids. This is the first example of the enantioselective 1,3-CH insertion reaction of magnesium carbenoid.     

Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

Rapid evaluation of molecular shape similarity index using pairwise calculation of the nearest atomic distances

Rapid evaluation method for obtaining molecular shape similarity index using pairwise calculation of the nearest atomic distance respected to the template atoms was investigated. This method for calculations of similarity indices remarkably reduced required time compared with hitherto methods (especially 2 or 3 orders of magnitude faster than the previous grid-based evaluation technique) and gave without clear loss of preciseness. The potential of these improvements and possible further enhancements are discussed.