The molecular network-guided exploration of the alkaloid extract of Callichilia inaequalis stems revealed a cluster attributed tentatively to dimeric monoterpene indole alkaloids of the rare criophylline subtype, initiating the dual study reported herein. A patrimonial-themed portion of this work was aimed at performing a spectroscopic reassessment of criophylline (1), a monoterpene bisindole alkaloid for which the nature of the inter-monomeric connectivity and configurational assignments have remained dubious. A targeted isolation of the entity annotated as criophylline (1) was undertaken to strengthen the available analytical evidence. An extensive set of spectroscopic data was acquired from the authentic sample of criophylline (1a) isolated earlier by Cavé and Bruneton. These spectroscopic studies proved the samples to be identical, and the complete structure of criophylline could be assigned, half a century after it was first isolated. The absolute configuration of andrangine (2) was also ascertained based on a TDDFT-ECD approach from the authentic sample. The forward-looking aspect of this investigation resulted in the characterization of two new criophylline derivatives from C. inaequalis stems, namely, 14′-hydroxycriophylline (3) and 14′-O-sulfocriophylline (4). Their structures, including absolute configurations, were elucidated by analysis of NMR and MS spectroscopic data and by ECD analysis. Notably, 14′-O-sulfocriophylline (4) is the first sulfated monoterpene indole alkaloid to have been reported. The antiplasmodial activity against the chloroquine-resistant strain of Plasmodium falciparum FcB1 was determined for criophylline and its two new analogues.

中文翻译：

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从真实生物碱样品的光谱重新评估到分子网络引导从卡奇利亚卡奇利亚 (Callichilia inaequalis) 中发现绿茶碱相关类似物

对卡奇利亚茎生物碱提取物的分子网络引导探索揭示了一个暂时归属于稀有叶绿碱亚型的二聚单萜吲哚生物碱的簇，启动了本文报道的双重研究。这项工作的一个以遗产为主题的部分旨在对氯茶碱 ( 1 ) 进行光谱重新评估，氯茶碱是一种单萜双吲哚生物碱，其单体间连接性和构型分配的性质仍然存在疑问。对注释为 criophylline ( 1 )的实体进行有针对性的分离，以加强现有的分析证据。从绿茶碱的真实样品中获得了一组广泛的光谱数据（1a）早些时候由 Cavé 和 Bruneton 分离出来。这些光谱研究证明了样品是相同的，并且在首次分离半个世纪后，可以确定叶绿碱的完整结构。还根据真实样品的 TDDFT-ECD 方法确定了安卓碱 ( 2 )的绝对构型。这项研究的前瞻性方面导致了来自C. inaequalis茎的两种新的绿茶碱衍生物的表征，即 14'-羟基绿茶碱 ( 3 ) 和 14'- O-磺茶碱 ( 4 )。通过 NMR 和 MS 光谱数据分析以及 ECD 分析阐明了它们的结构，包括绝对构型。值得注意的是，14'- O-sulfocriophylline ( 4 ) 是第一个被报道的硫酸化单萜吲哚生物碱。测定了叶绿碱及其两种新类似物对恶性疟原虫 FcB1耐氯喹菌株的抗疟原虫活性。