Tetrahedron Letters ( IF 1.5 ) Pub Date : 2019-02-02 , DOI: 10.1016/j.tetlet.2019.01.061 Mikio Fujii , Taiki Kuramochi , Yuhi Nakakuki , Rina Hatazawa , Kiju Konno , Tatsuo Munakata , Yasuaki Hirai
Gentianine is a metabolite of gentiopicroside and swertiamarin. Several biological activities have been reported for gentianine, such as antiinflammatory and antidiabetic activity, and hypotensive effect. Gentiopicroside is found in 0.9–9.8% content in Gentian root or Gentian scabra root, and Swertiamarin is contained in Swertia herb in 2–10%. These natural products can be potential starting materials for the synthesis of gentianine. This study describes the β-glucosidase-catalyzed hydrolysis of gentiopicroside and swertiamarin in the presence of hydroxylamine to afford gentianine N-oxide, which can be a synthetic precursor of gentianine derivatives. Enzymatic hydrolysis of swertiamarin selectively afforded gentianine N-oxide in 81% yield, whereas gentiopicroside afforded gentianine N-oxide and gentianol N-oxide. Plausible reaction pathways leading to gentianine, gentianol, and their N-oxides were also investigated.
中文翻译:
羟胺存在下酶促水解Swertiamarin合成龙胆碱N-氧化物及其与龙胆碱和龙胆醇的反应途径
龙胆碱是龙胆苦苷和苦味松的代谢产物。对于龙胆碱,已经报道了几种生物活性,例如抗炎和抗糖尿病活性以及降压作用。龙胆苷在龙胆根或龙胆子根中的含量为0.9–9.8%,而龙胆苦苷在龙胆草中的含量为2–10%。这些天然产物可能是合成龙胆碱的潜在原料。这项研究描述了在羟胺存在下,β-葡糖苷酶催化龙胆苦苷和苦味苦素水解,得到龙胆碱N-氧化物,它可以是龙胆碱衍生物的合成前体。Swertiamarin的酶水解选择性地以81%的产率提供了龙胆碱N-氧化物,而龙胆苦苷则提供了龙胆碱N-氧化物和庚醇N-氧化物。还研究了导致龙胆碱,龙胆醇及其氮氧化物的合理反应途径。