Internal Nucleophilic Catalyst Mediated Cyclisation/Ring Expansion Cascades for the Synthesis of Medium-Sized Lactones and Lactams
Internal Nucleophilic Catalyst Mediated Cyclisation/Ring Expansion Cascades for the Synthesis of Medium-Sized Lactones and Lactams
复制标题
内部亲核催化剂介导的环化/扩环级联用于合成中等大小的内酯和内酰胺
DOI：
10.1002/ange.201907206
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发表时间：
2019
影响因子：
--
通讯作者：
Lawer A
中科院分区：
文献类型：
--
作者：
Lawer A
描述了从线性前体合成中等大小内酯和内酰胺的策略，其中胺作为内部亲核催化剂以促进新的环化/扩环级联序列。这种方法避免了通常与中环环化方案相关的高稀释条件的需要，因为反应仅通过动力学上有利的“正常”大小的环状过渡态进行。该相同的特征还使得能够通过点到轴手性转移以完全的反选择性制备含联芳基的中等尺寸环。
A strategy for the synthesis of medium‐sized lactones and lactams from linear precursors is described in which an amine acts as an internal nucleophilic catalyst to facilitate a novel cyclisation/ring expansion cascade sequence. This method obviates the need for the high‐dilution conditions usually associated with medium‐ring cyclisation protocols, as the reactions operate exclusively via kinetically favourable “normal”‐sized cyclic transition states. This same feature also enables biaryl‐containing medium‐sized rings to be prepared with complete atroposelectivity by point‐to‐axial chirality transfer.