Efficient Route to (S)-Azetidine-2-carboxylic Acid

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概要

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• A new and efficient route to (S)-azetidine-2-carboxylic acid (>99.9% ee) in five steps and total yield of 48% via malonic ester intermediates was established. As the key step, efficient four-membered ring formation (99%) was achieved from dimethyl (S)-(1′-methyl)benzylaminomalonate by treating with 1,2-dibromoethane (1.5 eq) and cesium carbonate (2 eq) in DMF. Krapcho dealkoxycarbonylation of dimethyl (1′S)-1-(1′-methyl)benzylazetidine-2,2-dicarboxylate, the product of this cyclization procedure, proceeded with preferential formation (2.7:1, 78% total yield) of the desired (2S,1′S)-monoester, with the help of a chiral auxiliary which was introduced on the nitrogen atom. The undesired (2R,1′S)-isomer could be converted to that with proper stereochemistry, by a deprotonation and subsequent re-protonation step. Finally, lipase-catalyzed preferential hydrolysis of the (2S,1′S)-monoester and subsequent deprotection provided enantiomerically pure (S)-azetidine-2-carboxylic acid in a 91% yield from the mixture of (2S,1′S)- and (2R,1′S)-isomers.

• 2005-10-23

著者

• Kurokawa Masayuki

  Department of Radiology, Chiba University Hospital

• SUGAI Takeshi

  Department of Chemistry, Faculty of Science and Technology, Keio University

• NISHIYAMA Shigeru

  Department of Chemistry, Faculty of Science and Technology, Keio University

• Nishiyama Shigeru

  Department Of Chemistry Keio University

• Nishiyama Shigeru

  Department Of Chemistry Faculty Of Science And Technology Keio University

• Obata Rika

  Department Of Chemistry Keio University

• Obata Rika

  Department Of Chemistry Faculty Of Science And Technology Keio University

• Sugai Takeshi

  Department Of Agricultural Chemistry The University Of Tokyo

• FUTAMURA Yasuhiko

  Department of Chemistry, Keio University

• Kurokawa Masayuki

  Department Of Chemistry Keio University

• Futamura Yasuhiko

  Department Of Chemistry Keio University

• Nishiyama Shigeru

  Department Of Chemistry Faculty Of Science And Technology Keio Univerisity

• Nishiyama Shigeru

  Department of Applied Chemistry, Faculty of Engineering, Keio University

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