Unusual deoxygenation and reactivity studies related to O6-(benzotriazol-1-yl)inosine derivatives
Unusual deoxygenation and reactivity studies related to O6-(benzotriazol-1-yl)inosine derivatives
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DOI：
10.1021/jo7021795
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发表时间：
2008-02-15
影响因子：
3.6
通讯作者：
Lakshman, Mahesh K.
中科院分区：
文献类型：
--
作者：
Bae, Suyeal;Lakshman, Mahesh K.
报道了与 O-6-(苯并三唑-1-基)肌苷衍生物化学相关的新的和不寻常的进展。首先，开发了一种通过使用 PPh3/I-2/HOBt 进行合成的简单、可扩展的方法，并通过 P-31{H-1} NMR 对其进行了机械研究。然后研究了 O-6-(苯并三唑-1-基)肌苷核苷和双(频哪醇)二硼 (pinB-Bpin) 之间独特的氧转移反应，导致形成 C-6(苯并三唑-1-基)嘌呤核苷衍生物和 pinB-O-Bpin。该反应已通过 B-11{1H} NMR 进行了研究，并与通过 pinB-Bpin 氧化获得的 pinB-O-Bpin 进行了比较。 C-6（苯并三唑-1-基）嘌呤核苷的结构已通过 Pd 介导的溴代嘌呤核苷和 1H-苯并三唑之间的 C-N 键形成明确确定。最后，报道了 1,N-6-乙醇-和 1,N-6-丙-2'-脱氧腺苷的简短且极其简单的合成，以证明 O-6-(苯并三唑-1-基)肌苷核苷衍生物在组装相对复杂的化合物中的合成多功能性。
New and unusual developments related to the chemistry of O-6-(benzotriazol-1-yl)inosine derivatives are reported. First, a simple, scalable method for their syntheses via the use of PPh3/I-2/HOBt has been developed and has been mechanistically investigated by P-31{H-1} NMR. Studies were then conducted into a unique oxygen transfer reaction between O-6-(benzotriazol-1-yl)inosine nucleosides and bis(pinacolato)diboron (pinB-Bpin) leading to the formation of C-6 (benzotriazol-1-yl)purine nucleoside derivatives and pinB-O-Bpin. This reaction has been investigated by B-11{1H} NMR and compared to pinB-O-Bpin obtained by oxidation of pinB-Bpin. The structures of the C-6 (benzotriazol-1-yl)purine nucleosides have been unequivocally established via Pd-mediated C-N bond formation between bromo purine nucleosides and IH-benzotriazole. Finally, short and extremely simple synthesis of 1,N-6-ethano-and 1,N-6-propano-2'-deoxyadenosine are reported in order to demonstrate the synthetic versatility of the O-6-(benzotriazol-1-yl)inosine nucleoside derivatives for the assembly of relatively complex compounds.