Synthesis of alpha-keto-imides via oxidation of ynamides.
Synthesis of alpha-keto-imides via oxidation of ynamides.
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DOI：
10.1021/jo8015067
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发表时间：
2008-11-21
期刊：
影响因子：
--
通讯作者：
Zhao K
中科院分区：
文献类型：
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作者：
Al-Rashid ZF;Johnson WL;Hsung RP;Wei Y;Yao PY;Liu R;Zhao K
描述了通过 ynamide 氧化从头制备 α-酮酰亚胺。通过筛选多种炔氧化条件，已确定高效的 RuO2-NaIO4 介导的氧化和 DMDO 氧化可以耐受多种炔酰胺类型。除了获得多种 α-酮酰亚胺外，RuO2-NaIO4 方案还通过推拉炔酰胺的氧化以及来自甲硅烷基取代的炔酰胺的亚氨基酰基硅烷提供了进入邻位三羰基基序的新入口。使用 DMDO 可以实现含有烯烃的 ynamides 的化学选择性氧化，而 RuO2-NaIO4 方案则无效。这些研究为炔酰胺的合成用途提供了进一步的支持。
A de novo preparation of α-keto-imides via ynamide oxidation is described. With a number of alkyne oxidation conditions screened, a highly efficient RuO2-NaIO4 mediated oxidation and a DMDO oxidation have been identified to tolerate a wide range of ynamide types. In addition to accessing a wide variety of α-keto-imides, the RuO2-NaIO4 protocol provides a novel entry to the vicinal tricarbonyl motif via oxidation of push-pull ynamides, and imido acylsilanes from silyl-substituted ynamides. Chemoselective oxidation of ynamides containing olefins can be achieved using DMDO, while the RuO2-NaIO4 protocol is not effective. These studies provide further support for the synthetic utility of ynamides.