用于合成复杂生物碱的自由基介导的二聚化和氧化反应。
Radical-mediated dimerization and oxidation reactions for the synthesis of complex alkaloids.
作者信息
Lathrop Stephen P, Kim Justin, Movassaghi Mohammad
机构信息
Massachusetts Institute of Technology, Departement of Chemistry, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
出版信息
Chimia (Aarau). 2012;66(6):389-93. doi: 10.2533/chimia.2012.389.
Abstract
Concise and general strategies for radical-based dimerization of cyclotryptamine and cyclotryptophan derivatives in addition to radical-based oxidation of structurally complex diketopiperazines are discussed. The impact of these radical-based chemistries on the rapid generation of molecular complexity is highlighted using representative examples from recent complex homodimeric alkaloid total syntheses. Additionally, a new and general strategy for radical-based directed heterodimerization of cyclotryptamine substructures via solvent-caged unsymmetrical diazene fragmentation is discussed.
摘要
本文讨论了环色胺和环色氨酸衍生物基于自由基的二聚化以及结构复杂的二酮哌嗪基于自由基的氧化的简明通用策略。利用近期复杂同二聚体生物碱全合成的代表性实例，突出了这些基于自由基的化学反应对快速产生分子复杂性的影响。此外，还讨论了一种通过溶剂笼蔽的不对称重氮烷断裂实现环色胺亚结构基于自由基的定向异二聚化的新通用策略。
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