121(P64) Rhizopus delemar lipaseを活用した炭素環ヌクレオシドの不斉合成(ポスター発表の部)

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概要

• 論文の詳細を見る

• The application of enzyme to organic syntheses is one of the most useful and practical methods for the preparation of optically active compounds in high enantiomeric purities. Some hydrolytic enzymes, such as pig liver esterase (PLE), porcine pancreatic lipase (PPL), and Pseudomonas cepacia lipase (PFL, PCL, Amano PS) have been already reported as widely applicable enzymes for enantioselective hydrolysis of various substrates. However, there is a limit to the application of the previously known enzymes to the enantioselective hydrolysis of new substrates. We studied Rhizopus delemar lipase (RDL)-catalyzed asymmetric hydrolysis of meso-1,3-bis(acetoxymethyl)cyclopentane derivatives, which could be easily prepared from 7-substituted norbornadiene by a three-step sequence (ozonolysis, reduction, and acylation). It has become clear that the hydrolysis of meso-2-substituted-1,3-bis(acetoxymethyl)cyclopentanes using RDL afforded the monoalcohols 15-18 of high enantiomeric excess. As a synthetic application of this process, antiviral carbocyclic nucleosides such as (-)-carbovir, (-)-BCA and their analogues have been synthesized. RDL-catalyzed asymmetric hydrolysis was also applied for the synthesis of natural product (-)-curcumanolide A, which possesses the unique structure of three contiguous chiral centers and a spirolactone moiety. Unfortunately, hydrolysis of meso-diacetate 31 by RDL required prolonged reaction time (214 h), and the enantiomeric excess of the product (+)-36 was not satisfactory (86% ee). The enantiomeric excess of 36 was improved to >99% ee by PFL-catalyzed transesterification of meso-spirodiol 30 in n-octane-vinyl acetate. The formal synthesis of (-)-curcumanolide A was completed from the monoalcohol (-)-36.

• 1998-08-31

著者

• 田中 正一

  九大薬

• 末宗 洋

  九大薬

• 末宗 洋

  九州大学薬学部

• 末宗 洋

  九州大学大学院薬学府

• 乗嶺 吉彦

  九大薬

• 林 政樹

  九大薬

• 田中 正一

  長崎大学大学院医歯薬学総合研究科

• 末宗 洋

  九州大学大学院薬学研究院

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