Selective Molecular Transformation of 1, 2-Diols Based on Molecular Recognition

• Matsumura Yoshihiro

  Graduate School of Biomedical Sciences, Nagasaki University

• Onomura Osamu

  Graduate School of Biomedical Sciences, Nagasaki University

• Demizu Yosuke

  長崎大学大学院医歯薬学総合研究科生命薬科学専攻

Bibliographic Information

Other Title

• １，２‐ジオール分子認識に基づく選択的分子変換反応
• 1 2 ジオール ブンシ ニンシキ ニ モトズク センタクテキ ブンシ ヘンカン ハンノウ

Abstract

On the bases of the concept that a coordination of 1, 2-diols 1 with an appropriate metal ion (Mⁿ⁺) might form an activated five-membered intermediate in which the OH group is much activated than those of non-activated 1, we examined a monobenzoylation of 1 by benzoyl chloride using tin and copper ions as Mⁿ⁺. As the results, the monobenzoylation of 1 was achieved with high selectivity even in the presence of monools. The monobenzoylation reactions were then applied to kinetic resolution of dl-1 and asymmetric desymmetrization of meso-1 using a chiral organotin or BOX (bisoxazoline) -CuCl₂ as a catalyst. In particular, the asymmetric outcome using (R, R) -Ph-BOX-CuCl₂ catalyst was promising and attractive. That is, the kinetic resolution of dl-1 (with up to >99.9% ee for monobenzoylation of hydrobenzoin), its application to a synthesis of _D-inositol-1-phosphate (100% ee), the asymmetric desymmetrization of meso-1 (with up to 94% ee for monobenzoylation of meso-1, 2-hydrobenzoin and 93% ee for monocarbamoylation of meso-1, 2-cyclooctanediol), and the asymmetric desymmetrization of meso-1, 3-diols (with up to 55% ee for the monobenzoylation of ethyl 2-ethyl-2-hydroxymethyl-3-hydroxypropanoate) were achieved. Also, the method was applied to electrochemical oxidation of 1 and its asymmetric version (38% ee for the asymmetric desymmetrization of meso-hydrobenzoin and 72% ee for the kinetic resolution of dl-hydrobenzoin).

Journal

• Journal of Synthetic Organic Chemistry, Japan

  Journal of Synthetic Organic Chemistry, Japan 65 (3), 216-225, 2007

  The Society of Synthetic Organic Chemistry, Japan

Keywords

• molecular recognition
• 1, 2-diols
• kinetic resolution
• asymmetric desymmetrization
• benzoylation
• oxidation
• electrochemical oxidation

Details

• CRID: 1390282680289722624
• NII Article ID: 10018578272
• NII Book ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.65.216
• COI: 1:CAS:528:DC%2BD2sXjtFOjtro%3D
• ISSN: 18836526
• ISSN: 00379980
• HANDLE: 10069/16318
• NDL BIB ID: 8738349
• Web Site: https://nagasaki-u.repo.nii.ac.jp/records/20363
• Web Site: http://id.ndl.go.jp/bib/8738349
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I8738349
• Text Lang: ja
• Data Source:
  • JaLC
  • IRDB
  • NDL
  • Crossref
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed