N-allyl-N-sulfonyl ynamides as synthetic precursors to amidines and vinylogous amidines. An unexpected N-to-C 1,3-sulfonyl shift in nitrile synthesis.
N-allyl-N-sulfonyl ynamides as synthetic precursors to amidines and vinylogous amidines. An unexpected N-to-C 1,3-sulfonyl shift in nitrile synthesis.
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DOI：
10.1021/jo200780x
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发表时间：
2011-06-17
影响因子：
3.6
通讯作者：
Zhang, Yan-Shi
中科院分区：
文献类型：
--
作者：
DeKorver, Kyle A.;Johnson, Whitney L.;Zhang, Yu;Hsung, Richard P.;Dai, Huifang;Deng, Jun;Lohse, Andrew G.;Zhang, Yan-Shi
本文描述了从n -烯丙基- n -磺酰酰胺合成氨基的详细研究。从机理上讲，这是一个迷人的反应，由不同的途径组成，根据钯催化剂的氧化状态、胺的亲核性和配体的性质，可能导致去烯基化或烯基转移。它本质上构成了Pd(0)催化的n -烯丙基酰胺的aza-Claisen重排，这也可以通过热来完成。在对这些氮杂-克莱森重排进行热检查时，观察到n到c1,3 -磺酰基的移位。这是一种有用的合成腈的方法。虽然试图使这种1,3-磺酰基转移立体选择性失败，但我们发现了另一组串联异位重排，导致乙烯酰亚胺形成。总的来说，这项工作展示了使用这些酰胺可以发现的丰富的化学成分。
A detailed study of amidine synthesis from N-allyl-N-sulfonyl ynamides is described here. Mechanistically, this is a fascinating reaction consisting of diverging pathways that could lead to deallylation or allyl transfer depending upon the oxidation state of palladium catalysts, the nucleophilicity of amines, and the nature of the ligands. It essentially constitutes a Pd(0)-catalyzed aza-Claisen rearrangement of N-allyl ynamides, which can also be accomplished thermally. An observation of N-to-C 1,3-sulfonyl shift was made when examining these aza-Claisen rearrangements thermally. This represents a useful approach to nitrile synthesis. While attempts to render this 1,3-sulfonyl shift stereoselective failed, we uncovered another set of tandem sigmatropic rearrangements, leading to vinyl imidate formation. Collectively, this work showcases the rich array of chemistry one can discover using these ynamides.
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