芳基碘介导的缺电子烯烃电化学氮杂环丙烷化反应

doi:10.6023/cjoc202105046

摘要/Abstract

氮杂环丙烷在药物分子的设计合成中有广泛应用. 利用电化学方法合成氮杂环丙烷的研究主要集中于富电子烯烃的底物. 利用芳基碘化物介导, 以邻苯二甲酰肼为氮源, 在连通池中实现了缺电子烯烃的氮杂环丙烷化. 高价碘稳定的氮宾及酰化羟肼可能是原位产生的活性氮源试剂, 它们通过分步的过程实现三元环的构建. 一系列α,β-不饱和酯、酰胺、腈和酮都可以通过这个电化学方法转化为对应的氮杂环丙烷.

关键词: 电化学, 氮杂环丙烷, 高价碘, 缺电子烯烃

A protocol of electrochemical aziridination of electron-deficient alkenes was reported using phthalhydrazide as nitrogen source. The reaction could be conducted in undivided cell, and the ArI is essential to achieve the transformation. Hypervalent-iodine-stablized nitrene and acetyl hydroxyhydrazine were suggested as the in-situ generated nitrogen source for the stepwise aziridination. This protocol can be applied to the azirdination of α,β-unsaturated esters, amides, nitrile and ketones to give a series N-containing molecules.

Key words: electrochemistry, aziridination, hypervalent iodine, electron-deficient alkene

引用此文

刘峰, 戴洁, 程旭. 芳基碘介导的缺电子烯烃电化学氮杂环丙烷化反应[J]. 有机化学, 2021, 41(10): 4014-4020.

Feng Liu, Jie Dai, Xu Cheng. Aryl-Iodide-Mediated Electrochemical Aziridination of Electron-Deficient Alkenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 4014-4020.

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图/表 7

Scheme 1. Reaction design of aziridination of electron-deficient alkene

Entry	Deviation from standard conditions	Yield^b/%
1	None	67
2	ⁿBu₄NCl instead of ⁿBu₄NOAc	33
3	LiOAc instead of ⁿBu₄NOAc	37
4	ⁿBu₄NBF₄ instead of ⁿBu₄NOAc	Trace
5	1, 3, 5, 9 mA instead of 7 mA	35~57
6	EtOH, MeOH, THF, DMSO, DMF as solvent	ND
7	MeCN as solvent	33
8	No 4-MeOC₆H₄I (4)	ND
9	PhI instead of 4	Trace
10	4-FC₆H₄I instead of 4	Trace

Table 1. Optimization of aziridination of cinnamate mediated by ArIa

Scheme 2. Synthetic exploration of electrochemical aziridination reaction

Figure 1. CV analyses of reactants

Table 2. Substrate scope of aziridination of electron-deficient alkenea

Scheme 3. Experiments to investigate the reaction mechanism

Scheme 4. A plausible reaction mechanism for ArI-mediated electrochemical aziridination

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