重氮导向片段组装在（+）-去甲基- - 腊梅碱及相关异二聚体生物碱的全合成和立体化学归属中的应用
Application of diazene-directed fragment assembly to the total synthesis and stereochemical assignment of (+)-desmethyl--chimonanthine and related heterodimeric alkaloids.
作者信息
Lathrop Stephen P, Movassaghi Mohammad
机构信息
Massachusetts Institute of Technology, Department of Chemistry, Cambridge, Massachusetts 02139, USA.
出版信息
Chem Sci. 2014 Jan 1;5(1). doi: 10.1039/C3SC52451E.
Abstract
We describe the first application of our methodology for heterodimerization via diazene fragmentation towards the total synthesis of (-)-calycanthidine, -chimonanthine, and (+)-desmethyl--chimonanthine. Our syntheses of these alkaloids feature an improved route to C3a-aminocyclotryptamines, an enhanced method for sulfamide synthesis and oxidation, in addition to a late-stage diversification leading to the first enantioselective total synthesis of (+)-desmethyl--chimonanthine and its unambiguous stereochemical assignment. This versatile strategy for directed assembly of heterodimeric cyclotryptamine alkaloids has broad implications for the controlled synthesis of higher order derivatives with related substructures.
摘要
我们描述了我们通过重氮烯断裂实现异二聚化的方法首次应用于（-）-加州樟碱、（-）-腊梅碱和（+）-去甲基-（-）-腊梅碱的全合成。我们对这些生物碱的合成具有改进的C3a-氨基环色胺合成路线、增强的磺胺合成和氧化方法，此外还有后期多样化策略，实现了（+）-去甲基-（-）-腊梅碱的首次对映选择性全合成及其明确的立体化学归属。这种用于定向组装异二聚环色胺生物碱的通用策略对具有相关亚结构的高阶衍生物的可控合成具有广泛意义。
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