二碘化钐促进的2-哌啶酮与α,β-不饱和酸酯的加成-开环反应研究

doi:10.6023/cjoc202106040

有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4320-4326.DOI: 10.6023/cjoc202106040 上一篇下一篇

研究论文

二碘化钐促进的2-哌啶酮与α,β-不饱和酸酯的加成-开环反应研究

孙建婷^a^,^b, 陈玲艳^a^,^*(), 魏邦国^b

a 上海工程技术大学化学化工学院上海 201620
b 复旦大学药学院上海 201203

收稿日期:2021-06-22 修回日期:2021-07-20 发布日期:2021-08-24
通讯作者: 陈玲艳
基金资助:
研究生创新(20KY0431)

Samarium Diiodide Promoted the Addition-Ring-Opening Reaction of 2-Piperidinone with α,β-Unsaturated Esters

Jian-Ting Sun^a^,^b, Ling-Yan Chen^a(), Bang-Guo Wei^b

a College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620
b School of Pharmacy, Fudan University, Shanghai 201203

Received:2021-06-22 Revised:2021-07-20 Published:2021-08-24
Contact: Ling-Yan Chen
Supported by:
Postgraduate Students Innovation Program(20KY0431)

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1. 0253-2786-41-11-4320辅助材料.pdf(1381KB)

摘要/Abstract

以^tBuOH作为质子供体, 基于SmI₂促进2-哌啶酮与α,β-不饱和酸酯进行自由基加成-开环反应, 以43%~89%的收率制备了一系列含N-Boc氨基酮化合物3a~3l. 以(S)-8-[(叔丁氧基羰基)氨基]-5-[(叔丁基二甲基甲硅烷基)氧基]-4-氧代辛酸甲酯(3e)为关键中间体, 经一锅去保护-环合-还原-胺解等反应建立了吲哚里西啶骨架(6)的合成方法.

关键词: 二碘化钐, 2-哌啶酮, 自由基加成-开环反应, 吲哚里西啶

A convenient approach to N-Boc amino ketones 3a~3l has been developed, which features a SmI₂ prompted one-pot radical addition-ring opening process of 2-piperidinone with α,β-unsaturated esters. Moreover, the indolizidine skeleton (6) has been successfully synthesized from the key methyl (S)-8-((tert-butoxycarbonyl)amino)-5-((tert-butyl- dimethylsilyl)oxy)-4-oxooctanoate (3e), which undergoes one-pot deprotection-condensation-reduction-amination process.

Key words: samarium diiodide, 2-piperidinone, radical addition-ring opening, indolizidine

引用此文

孙建婷, 陈玲艳, 魏邦国. 二碘化钐促进的2-哌啶酮与α,β-不饱和酸酯的加成-开环反应研究[J]. 有机化学, 2021, 41(11): 4320-4326.

Jian-Ting Sun, Ling-Yan Chen, Bang-Guo Wei. Samarium Diiodide Promoted the Addition-Ring-Opening Reaction of 2-Piperidinone with α,β-Unsaturated Esters[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4320-4326.

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图/表 6

图1. 几种含有羟基吲哚里西啶骨架的天然分子

Figure 1. Several natural molecules containing hydroxyindolizidine skeleton

Entry	Additive (equiv.)	Temp./℃	Time/h	Yield^b/%
1	—	–78~–50	2	31
2	H₂O (4)	–78~–50	2	12
3	H₂O (100)	r.t.	0.5	23
4	MeOH (4)	–78~–50	2	Trace
5	^tBuOH (4)	–78~–50	2	68
6	^tBuOH (4)	–78	2	40

表1. 反应条件优化a

Table 1. Optimization of reaction conditions

图式1. 2-哌啶酮1b~1e的合成路线

Scheme 1. Synthetic route of 2-piperidinone 1b~1e

表2. 反应底物拓展a

Table 2. Reaction substrate expansion

图式2. 羟基吲哚里西啶分子的合成

Scheme 2. Synthesis of hydroxyindolizidine Reagents and conditions: (a) (1) TFA, DCM, 0 ℃, 8 h; (2) Pd/C, H2, TEA, 48 h. two steps 68%. (b) LDA, PhSeBr, THF, –78 ℃, 65%.(c) H2O2, r.t., 1 h, 64%. (d) LiAlH4, AlCl3, THF, –78 ℃, 2 h, 79%.(e) NaIO4 or H2O2, r.t., 1 h

图2. 化合物(S)-5的晶体结构

Figure 2. Crystal structure of compound (S)-5

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二碘化钐促进的2-哌啶酮与α,β-不饱和酸酯的加成-开环反应研究

Samarium Diiodide Promoted the Addition-Ring-Opening Reaction of 2-Piperidinone with α,β-Unsaturated Esters

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