Lewis base catalysis of bromo- and iodolactonization, and cycloetherification
Lewis base catalysis of bromo- and iodolactonization, and cycloetherification
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DOI：
10.1073/pnas.1005296107
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发表时间：
2010-11-30
影响因子：
11.1
通讯作者：
Burk, Matthew T.
中科院分区：
文献类型：
--
作者：
Denmark, Scott E.;Burk, Matthew T.
发展了刘易斯碱催化的溴代和碘代内酯化反应，系统地考察了催化剂结构对反应速率和环化选择性的影响。底物结构对卤代内酯化反应的影响和这些影响与催化剂结构的影响的相互作用进行了研究，导致环化选择性的综合有用的改进。所获得的知识应用于刘易斯碱催化的溴代和碘代环醚化反应的发展。一些调查的催化剂的能力，以影响卤代内酯化反应的环化选择性，证明了它们的存在下，在过渡结构的产品决定环化步骤。这一观察结果意味着，无论卤离子外消旋化的速率或机制如何，这些催化剂的手性衍生物都有可能提供对映体富集的产物。
Lewis base catalyzed bromo- and iodolactonization reactions have been developed and the effects of catalyst structure on rate and cyclization selectivity have been systematically explored. The effects of substrate structure on halolactonization reactions and the interaction of those effects with the effects of catalyst structure have been investigated, leading to synthetically useful improvements in cyclization selectivity. The knowledge acquired was applied to the development of Lewis base catalyzed bromo- and iodocycloetherification reactions. The ability of some of the surveyed catalysts to influence the cyclization selectivity of halolactonization reactions demonstrates their presence in the transition structure of the product-determining cyclization step. This observation implies that chiral derivatives of these catalysts have the potential to provide enantioenriched products regardless of the rates or mechanisms of halonium ion racemization.