首页> 外文期刊>Journal of molecular catalysis, B. Enzymatic >The anomalous course of the microsomal transformation of the exo-2,3-epoxides of norbornene and norbornadiene. The possible involvement of a general acid activation during the enzymatic hydrolysis of these oxides
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The anomalous course of the microsomal transformation of the exo-2,3-epoxides of norbornene and norbornadiene. The possible involvement of a general acid activation during the enzymatic hydrolysis of these oxides

机译:降冰片烯和降冰片二烯的exo-2,3-环氧化物微粒体转化的异常过程。这些氧化物的酶促水解过程中可能涉及一般的酸活化

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摘要

The enzymatic hydrolysis of exo-2,3-epoxy-norbornane (1) with a crude rabbit liver microsomal preparation occurred with a rearrangement and gave selectively (2R,7S)-bicyclo[2.2.1]heptane-2,7-diol (3), enantiomeric excess (ee) 30+2%. The analogous exo-2,3-epoxy-5-norbornene (2) gave, under the same conditions, exclusively endo-6-hydroxymethylbicyclo[3.1.0]hex-2-ene (4), arising from the microsomal catalyzed reduction of the first formed endo-6-formylbicyclo[3.1.0]hex-2-ene (5). A mechanistic explanation for the observed products is proposed.
机译:粗制兔肝微粒体制剂对exo-2,3-epoxy-norbornane(1)的酶水解发生了重排,并选择性地产生了(2R,7S)-双环[2.2.1]庚烷-2,7-二醇( 3),对映体过量(ee)30 + 2%。在相同条件下,类似的exo-2,3-环氧-5-降冰片烯(2)仅由微粒体催化的三聚氰胺的还原反应生成内聚6-羟甲基双环[3.1.0]己-2-烯(4)。首先形成了内6-甲酰基双环[3.1.0]己-2-烯(5)。提出了对所观察产品的机械解释。

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