title: "Marking" the nitrogen atoms of phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)-methane. Synthesis and absolute configuration of the corresponding tris(pyridine N-oxide).
abstract: To "mark" the nitrogen atoms in phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)methane (1), we have synthesized the corresponding tris(pyridine N-oxide) 2 by oxidation of 1 with m-chloroperbenzoic acid. The nitrogen atoms of 2 are unequivocally determined by the X-ray crystal analysis of a single crystal of rac-2 whereas the nitrogen atoms cannot be assigned at all in the case of rac-1. N-Oxide 2 can be resolved by chiral high-performance liquid chromatography under similar conditions to those used for the resolution of 1. The calculated circular dichroism (CD) curve for (R)-2 on the basis of time-dependent density functional theory reproduces the experimental spectra very well to suggest that the second-eluted fraction ([CD(+)283]-2) is the R isomer, namely (R)-[CD(+)283]-2. The independent absolute configuration determinations for 1 and 2 are in keeping with the chemical correlation between the two compounds by oxidation of (R)-1 into (R)-2.
authors.affiliation: Department of Chemistry, Graduate School of Science, Osaka University, Osaka, Japan. kmatsu@chem.sci.osaka-u.ac.jp
authors.forename: Kouzou
authors.initials: K
authors.lastname: Matsumoto
authors.forename: Kaori
authors.initials: K
authors.lastname: Miki
authors.forename: Takuya
authors.initials: T
authors.lastname: Inagaki
authors.forename: Tatsuo
authors.initials: T
authors.lastname: Nehira
authors.forename: Gennaro
authors.initials: G
authors.lastname: Pescitelli
authors.forename: Yasukazu
authors.initials: Y
authors.lastname: Hirao
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Kurata
authors.forename: Takeshi
authors.initials: T
authors.lastname: Kawase
authors.forename: Takashi
authors.initials: T
authors.lastname: Kubo
mesh_terms: D003497:Cyclic N-Oxides / Q000138:chemical synthesis* / Q000737:chemistry* / Q000302:isolation & purification; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D055620:Optical Phenomena; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry* / Q000302:isolation & purification; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D003497:Cyclic N-Oxides; D011725:Pyridines; C561908:phenyl-(2-pyridyl)-(3-pyridyl)-(4-pyridyl)-methane; C561909:tris(pyridine N-oxide); D009584:Nitrogen; D008697:Methane