Complete stereodivergence in the synthesis of 2-amino-1,3-diols from allenes
Complete stereodivergence in the synthesis of 2-amino-1,3-diols from allenes
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DOI：
10.1039/c4sc01214c
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发表时间：
2014-01-01
期刊：
影响因子：
8.4
通讯作者：
Schomaker, Jennifer M.
中科院分区：
文献类型：
--
作者：
Adams, Christopher S.;Grigg, R. David;Schomaker, Jennifer M.
含胺的立体三联体(‘三联体’)是许多生物活性天然产物的关键基元，其中氮被嵌入到三个连续的、含杂原子的手性碳的阵列中。丙二烯氮杂化反应提供了方便地获得胺三元化合物的途径，在那里氮的位置和伴随的杂原子的身份可以很容易地被操纵。然而，立体化学的灵活性，即单一的丙二烯可以选择性地转化为特定三元化合物的任何可能的非对映异构体，一直难以捉摸。在这里，我们描述了研究，以了解试剂和底物控制如何有效地用于二烯的立体发散氧化胺化，通过在每个可能的非对映异构体2-氨基-1，3-二醇产物中将富含对映体的前体的轴向手性转移到点手性。还介绍了这一灵活的策略在天然产物脱毒碱的所有四个立体异构体的合成中的应用。
Amine-containing stereotriads ('triads'), where the nitrogen is embedded in an array of three contiguous, heteroatom-bearing chiral carbons, are key motifs in numerous bioactive natural products. Allene aziridination provides convenient access to amine triads where the position of the nitrogen and the identities of the accompanying heteroatoms can be readily manipulated. However, stereochemical flexibility, where a single allene can be selectively transformed into any possible diastereomer of a specific triad, has been elusive. Herein, we describe studies to understand how both reagent and substrate control can be effectively employed in the stereodivergent oxidative amination of allenes, with transfer of the axial chirality of an enantioenriched precursor to point chirality in each possible diastereomeric 2-amino-1,3-diol product. Application of this flexible strategy to the synthesis of all four stereoisomers of the natural product detoxinine is also presented.