WestCHEM, School of Chemistry, The Joseph Black Building, University of Glasgow, Glasgow, UK G12 8QQ.
Org Biomol Chem. 2011 Oct 7;9(19):6761-70. doi: 10.1039/c1ob05833a. Epub 2011 Aug 12.
A new flexible approach for the stereoselective synthesis of substituted 1H-pyrrol-2(5H)-ones and 3,6-dihydro-1H-pyridin-2-ones has been developed. The general strategy employed the stereoselective reduction of a series of α,β-unsaturated ketones under chelation control to give the corresponding allylic alcohols. Overman rearrangement to install the key C-N bond followed by conversion to either prop-2-enoyl or but-3-enoyl derivatives and a ring closing metathesis reaction gave the target unsaturated γ- and δ-lactams. The synthetic utility of these compounds as building blocks was demonstrated by the preparation of the N-Boc derivative of (-)-coniine.
一种新的用于取代的 1H-吡咯-2(5H)-酮和 3,6-二氢-1H-吡啶-2-酮的立体选择性合成的灵活方法已经开发出来。该通用策略采用在螯合控制下对一系列α,β-不饱和酮进行立体选择性还原，得到相应的烯丙醇。Overman 重排引入关键的 C-N 键，然后转化为丙-2-烯酰基或丁-3-烯酰基衍生物，并进行环闭合复分解反应，得到目标不饱和γ-和δ-内酰胺。这些化合物作为构建块的合成实用性通过（-）coniine 的 N-Boc 衍生物的制备得到了证明。
