Asymmetric Synthesis of Novel gem-Difluorinated Compounds Using Chemo-Enzymatic Methodology.

DOI Web Site 2 Citations 79 References
  • Itoh Toshiyuki
    Department of Chemistry, Faculty of Education, Okayama University

Bibliographic Information

Other Title
  • Ｃｈｅｍｏ‐Ｅｎｚｙｍａｔｉｃ合成法によるジフルオロメチレン基を有するキラル化合物の合成
  • Chemo Enzymatic ゴウセイホウ ニ ヨル ジフルオロメチレンキ オ ユウスル キラル カゴウブツ ノ ゴウセイ

Search this article

Abstract

Asymmetric synthesis of two types of partly difluorinated compounds has been accomplished based on the chemo-enzymatic reaction strategy. Optically active 1, 1-difluoro-2, 3- (bishydroxymethyl) cyclopropane has been synthesized through lipase-catalyzed reaction; prochiral diacetate of cis-1, 1-difluoro-2, 3-bis (hydroxymethyl) cyclopropane was converted to the corresponding monoacetate through Alcaligenes sp. lipase-catalyzed hydrolysis with >99% enantiomeric excess. Racemic acetate of trans-1, 1-difluoro-2, 3-bis (hydroxymethyl) cyclopropane was resolved by Pseudomonas sp. lipase-catalyzed hydrolysis successfully. Lipase-catalyzed reaction was employed to resolve bis-difluorocyclopropane derivatives; the first synthesis of optically pure (trans, trans) -2, 2, 5, 5-tetrafluoro-1, 6-bis (hydroxymethyl) bicyclopropane has thus been accomplished. Carbon radicals from allyl O-trimethylsilyl-α-bromo-α, α-difluoroacetal can cyclize onto the olefinic part regiospecifically to give γ-lactols in good yield. The lactols are then converted to the corresponding α, α-difluoro-γ-lactones. Systematic synthesis of multifluorinated-α, α-difluoro-γ-lactones has been accomplished through intramolecular radical cyclization as a key reaction. The synthesis of difluorinated analogue of an insect sex pheromone has been accomplished through intramolecular radical cyclization and lipase-catalyzed reaction.

Journal

Citations (2)*help

See more

References(79)*help

See more

Keywords

Details 詳細情報について

Report a problem

Back to top