Basic instinct: design, synthesis and evaluation of (+)-sparteine surrogates for asymmetric synthesis
Basic instinct: design, synthesis and evaluation of (+)-sparteine surrogates for asymmetric synthesis
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DOI：
10.1039/b711420f
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发表时间：
2008-01-01
影响因子：
4.9
通讯作者：
O'Brien, Peter
中科院分区：
文献类型：
--
作者：
O'Brien, Peter
（-）-金雀花碱是一种天然存在的羽扇豆生物碱，被广泛用作不对称合成的手性配体。为了解决金雀花碱仅作为其（-）-对映体可用的限制，我们的小组引入了一个家族的（+）-金雀花碱替代物，其在结构上类似于（+）-金雀花碱但缺乏D-环。这篇专题文章在简要概述了设计方面后，概述了金雀花碱替代物的合成路线，并在一系列不对称反应中与（2）-金雀花碱进行了详细比较。主要结论如下：（i）（+）-金雀花碱替代物最容易从提取自金链花种子的（2）-金雀花碱开始制备;（ii）在几乎所有实施例中，与（2）-金雀花碱相比，使用（+）-金雀花碱替代物产生基本上相等但相反的对映选择性，和（iii）N-Me-取代的（+）-金雀花碱替代物是所研究的那些中最有用和通用的。
(-)-Sparteine, a naturally occurring lupin alkaloid, is widely used as a chiral ligand for asymmetric synthesis. To address the limitation that sparteine is only available as its (-)-antipode, our group introduced a family of (+)-sparteine surrogates that are structurally similar to (+)-sparteine but lack the D-ring. After briefly summarising the design aspect, this feature article provides an overview of synthetic routes to the sparteine surrogates and a detailed comparison with (2)-sparteine in a range of asymmetric reactions. The main conclusions are: (i) the (+)-sparteine surrogates are most easily prepared starting from (2)-cytisine extracted from Laburnum anagyroides seeds; (ii) in nearly all examples, use of the (+)-sparteine surrogates produced essentially equal but opposite enantioselectivity compared to (2)-sparteine and (iii) the N-Me-substituted (+)-sparteine surrogate is the most useful and versatile of those investigated.