Further Studies on the Direct Synthesis of alpha, beta-Unsaturated Ketimines and alpha, beta-Enones by Chemoselective Dehydrative Addition of Functionalized Alkenes to Secondary Amides
Further Studies on the Direct Synthesis of alpha, beta-Unsaturated Ketimines and alpha, beta-Enones by Chemoselective Dehydrative Addition of Functionalized Alkenes to Secondary Amides
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功能化烯烃与仲酰胺化学选择性脱水加成直接合成α,β-不饱和酮亚胺和α,β-烯酮的进一步研究
DOI：
10.1002/cjoc.201600700
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发表时间：
2017
影响因子：
5.4
通讯作者：
Huang Ying-Hong
中科院分区：
文献类型：
--
作者：
Huang Pei-Qiang;Huang Ying-Hong
本文介绍了C-H烷基亚胺化反应和烯烃与仲酰胺酰化反应的研究结果。亲核配偶体已经扩展到涵盖一系列带有官能团的官能化烯烃，包括酯，α，β-不饱和酯，不拥挤的酮基团，以及乙醛的烯醇衍生物，如烯醇醚和烯酰胺。亲电伙伴已从N-（2，6-二甲基苯基）和N-甲基酰胺扩展到N-正丁基和N-环己基酰胺。结果表明，该方法可以高效、高产率、一锅法合成多种功能化的α，β-不饱和酮亚胺和α，β-烯酮。该方法被应用于（E）-6-苯乙烯基四氢-2H-吡喃-2-酮（5）的简明合成，（E）-6-苯乙烯基四氢-2H-吡喃-2-酮（5）是合成一系列苯乙烯基内酯天然产物的直接中间体，包括（±）-goniothalamine（6）、（±）-goniothalamine oxide（7）、（±）-goniodiol（8）、（±）-leiocarpin A（9）、（±）-9-deoxygoniopyrone（10）和（±）-7-epi-goniodiol（11）。
Described in this paper are the results of an investigation on the extension of the C‐H alkyliminylation and acylation of alkenes with secondary amides. The nucleophilic partner has been extended to cover a series of functionalized alkenes bearing functional groups including ester,α,β‐unsaturated ester, uncongested ketone groups, as well as enol derivatives of acetaldehyde such as enol ether and enamides. The electrophilic partner has been extended fromN‐(2,6‐dimethylphenyl) andN‐methyl amides toN‐n‐butyl, andN‐cyclohexyl amides. The results demonstrated that the method can be used to synthesize a number of functionalizedα,β‐unsaturated ketimines andα,β‐enones in an efficient, high yielding, and one‐pot manner. The method was applied to a concise synthesis of (E)‐6‐styryltetrahydro‐2H‐pyran‐2‐one (5), an immediate intermediate in the syntheses of a series of styryllactone natural products including (±)‐goniothalamine (6), (±)‐goniothalamine oxide (7), (±)‐goniodiol (8), (±)‐leiocarpin A (9), (±)‐9‐deoxygoniopypyrone (10), and (±)‐7‐epi‐goniodiol (11).