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Proceedings of the Japan Academy, Ser. B, Physical and Biological Sciences

Vol. 91 No. 8 (2015)

  Vol. 91 No. 8 (2015)
Influenza virus pathogenicity regulated by host cellular proteases, cytokines and metabolites, and its therapeutic options
Hiroshi KIDO
Proc. Jpn. Acad., Ser. B, Vol. 91, 351-368 (2015) [Abstract and Full Text]
Catalytic enantioselective synthesis of chiral organic compounds of ultra-high purity of >99% ee
Ei-ichi NEGISHI and Shiqing XU
Proc. Jpn. Acad., Ser. B, Vol. 91, 369-393 (2015) [Abstract and Full Text]
Discovery of m7G-cap in eukaryotic mRNAs
Proc. Jpn. Acad., Ser. B, Vol. 91, 394-409 (2015) [Abstract and Full Text]
Genetic studies of rheumatoid arthritis
Kazuhiko YAMAMOTO, Yukinori OKADA, Akari SUZUKI and Yuta KOCHI
Proc. Jpn. Acad., Ser. B, Vol. 91, 410-422 (2015) [Abstract and Full Text]
The mucosal immune system: From dentistry to vaccine development
Hiroshi KIYONO and Tatsuhiko AZEGAMI
Proc. Jpn. Acad., Ser. B, Vol. 91, 423-439 (2015) [Abstract and Full Text]
Original Article
Whole-body counter surveys of over 2700 babies and small children in and around Fukushima Prefecture 33 to 49 months after the Fukushima Daiichi NPP accident
Ryugo S. HAYANO, Masaharu TSUBOKURA, Makoto MIYAZAKI, Akihiko OZAKI, Yuki SHIMADA, Toshiyuki KAMBE, Tsuyoshi NEMOTO, Tomoyoshi OIKAWA, Yukio KANAZAWA, Masahiko NIHEI, Yu SAKUMA, Hiroaki SHIMMURA, Junichi AKIYAMA and Michio TOKIWA
Proc. Jpn. Acad., Ser. B, Vol. 91, 440-446 (2015) [Abstract and Full Text]
Cover Illustration
Catalytic Enantioselective Synthesis of Chiral Organic Compounds of Ultra-high Purity of >99% ee
  Chirality plays a vital role in chemical, biological, pharmaceutical, and material sciences. Despite recent advances in asymmetric synthesis, the preparation of enantiomerically pure compounds had remained until recently as a significant challenge to synthetic organic chemists.
  In 1978, Professor Negishi discovered “Zr-catalyzed alkyne carboalumination” (Alkyne ZACA) and this reaction has since been widely used as a powerful tool for various natural product syntheses. Its mechanistic studies have revealed that this reaction involves acyclic carbometalation with “super-acidic” bimetallic reagents generated in situ through interactions between two Lewis acids, i.e., alkylalanes and 16-electron zirconocene derivatives, affectionately termed as the “two-is-better-than-one” principle.
  With this notion in mind, Professor Negishi further discovered Zr-catalyzed asymmetric carboalumination of alkenes (ZACA), an as yet rare catalytic asymmetric C–C bond-forming reaction of terminal alkenes of “one-point-binding” without requiring any other functional groups. ZACA reaction has since “revolutionized” the syntheses of a wide variety of chiral natural products including deoxypolypropionates, isoprenoids, and many other natural and non-natural compounds of biological and medicinal interest. Professor Negishi recently developed a quite unique coupling of ZACA–Lipase-catalyzed acetylation–Transition metal-catalyzed cross-coupling processes, as illustrated in the cover scheme, which provides a widely applicable and efficient method for preparing a variety of chiral organic compounds of “ultra-high” purity levels (>99% ee). This approach certainly opens a new horizon for asymmetric synthesis.
Hisashi Yamamoto
Professor and Director of Molecular Catalyst Research Center
Chubu University

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