メゾアリールサブポルフィリンの化学

京都大学0048新制・課程博士博士(理学)甲第17941号理博第3911号新制||理||1564(附属図書館)30771京都大学大学院理学研究科化学専攻(主査)教授 大須賀 篤弘, 教授 丸岡 啓二, 教授 時任 宣博学位規則第4条第1項該当Doctor of ScienceKyoto UniversityDGA

Boron Arylations of Subporphyrins with Aryl Zinc Reagents

Boron arylations of B‐(methoxo)triphenylsubporphyrin have been developed with a combined use of ArZnI⋅LiCl and trimethylsilyl chloride. Aryl zinc reagents bearing bromo, cyano, amide, and ester groups can be employed for the B‐arylation reaction to provide the corresponding B‐arylated subporphyrins in moderate yields. Postmodifications of B‐arylated subporphyrins have been demonstrated without loss of the B−C bond. These modifications include conversion of the cyano group into a benzoyl group with PhMgBr, hydrolysis of the ester group to give B‐(4‐carboxyphenyl)subporphyrin, and Pd‐catalyzed Suzuki–Miyaura coupling of the 4‐bromophenyl group to give a 1,4‐phenylene‐bridged subporphyrin–ZnII porphyrin hybrid that displays intramolecular excitation energy transfer from the subporphyrin to the porphyrin. The newly synthesized B‐arylated subporphyrins have been fully characterized by NMR, UV/Vis absorption and fluorescence spectroscopies, mass spectrometry, electrochemical measurements, and X‐ray diffraction analysis.Bonding B to C: Boron arylations of B‐(methoxo)triphenylsubporphyrin have been developed with a combined use of ArZnI⋅LiCl and trimethylsilyl chloride (TMSCl; see scheme), which allow the synthesis of B‐aryl subporphyrins bearing bromo, cyano, amide, and ester groups. Postmodifications of the B‐aryl subporphyrins have been demonstrated without loss of the B−C bond. Newly synthesized B‐arylated subporphyrins have been fully characterized.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137618/1/chem201504719.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137618/2/chem201504719-sup-0001-misc_information.pd