基于氨甲酰基硅烷的β-硝基酰胺衍生物的合成

doi:10.6023/cjoc202206014

摘要/Abstract

用氨甲酰基硅烷作氨甲酰基源, 对α-硝基-2-烯酸乙酯进行直接氨酰基化反应, 在不加催化剂温和条件下, 可以53%~96%的分离收率得到β-硝基酰胺衍生物. 此方法底物(或官能团)适用范围广, 在双键上可连接脂肪烃基、芳香烃基、杂芳香烃基和不饱和芳香烃基. 通过不同结构的氨甲酰基硅烷的选择, 此方法可合成β-硝基叔酰胺和甲氧甲基保护的仲酰胺衍生物. 该合成方法具有反应条件温和、产物收率较高、副产物较少、立体选择性较强以及后处理容易等优点, 既是一种制备β-硝基酰胺衍生物的新方法, 也是进一步合成具有潜在应用价值的β-氨基酰胺的新方法.

关键词: 亲核加成, 氨甲酰基硅烷, β-硝基烯烃, 氨酰化, β-硝基酰胺

Using carbamoylsilane as an carbamoyl source, the direct aminocarbonylation of α-nitro-2-enoic acid ethyl ester afforded β-nitroamide derivatives in 53%~96% separation yields under mild conditions without use of catalysts. The protocol has a wide range of substrates (or functional groups), tolerated a nitroalkenes bearing different groups on the C=C bond such as aliphatic group, aryl, hetero aryl and unsaturated aryl. This procedure allows the preparation of various β-nitroamides including β-nitro tertiary amide derivatives and methoxymethyl-protecting β-nitro secondary amide derivatives by the selection of various carbamoylsilanes. The synthesis method has the advantages of mild reaction conditions, good to excellent yields, less by-products, strong stereoselectivity and easy post-processing. It is a new method for preparing β-nitroamide derivatives and then synthesizing β-aminoamides with potential application value.

Key words: nucleophilic addition, carbamoylsilanes, β-nitroalkenes, aminocarbonylation, β-nitroamides

引用此文

李俊飞, 韩宇玲, 刘艳红, 陈建新. 基于氨甲酰基硅烷的β-硝基酰胺衍生物的合成[J]. 有机化学, 2022, 42(11): 3880-3889.

Junfei Li, Yuling Han, Yanhong Liu, Jianxin Chen. Synthesis of β-Nitroamide Derivatives Based on Carbamoylsilane[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3880-3889.

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图/表 7

图式1. 基于氨甲酰基硅烷作为氨甲酰基源的氨甲酰基化反应

Scheme 1. Aminocarbonylation based on carbamoylsilane as an carbamoyl source

图式2. 硝基烯烃与氨甲酰基硅烷反应合成β-硝基酰胺衍生物

Scheme 2. Synthesis of β-nitroamide derivatives by reaction of carbamoylsilanes with nitroalkenes

Entry	Solvent	Temp./℃	Time^a/h	Yield^b^,^c/%
1	CH₂Cl₂	35	21	45
2	THF	60	10	69
3	MeCN	60	11	63
4	PhH	60	12	73
5	PhMe	60	9	85
6	PhMe	80	8	80
7	PhMe	100	7	74

表1. 溶剂和温度对硝基烯烃与氨甲酰基硅烷反应的影响

Table 1. Solvent and temperature effects on reaction of nitroalkenes with carbamoylsilane

Entry	β-Nitroalkene	Carbamoylsilane	Product		Time^a/h		Yield^b^,^c/%
1					10		83
2					18		89
3					25		64
4					23		76
5					27		75
Entry	β-Nitroalkene	Carbamoylsilane	Product	Time^a/h		Yield^b^,^c/%
6					9		85
7				8		95
8				6		96
9				9		80
10				13		79
11				7		82
12				6		85
13				19		53
14				17		64
15				10		68
Entry	β-Nitroalkene	Carbamoylsilane	Product	Time^a/h		Yield^b^,^c/%
16				10		80
17				8		82
18				15		71

表2. 硝基烯烃1与氨甲酰基硅烷2或4反应合成β-硝基酰胺衍生物3或5

Table 2. Synthesis of β-nitroamide derivatives 3 or 5 from β-nitroalkenes 1 and carbamoylsilanes 2 or 4

图式3. 产物5在酸性中水解生成β-硝基-β-乙氧羰基仲酰胺

Scheme 3. Formation of β-nitro-β-ethoxycarbonyl secondary amides by acid hydrolysis of 5

图1. 化合物3f的晶体结构

Figure 1. Crystal structure of compound 3f

图式4. 氨甲酰基硅烷与硝基烯烃反应的可能机理

Scheme 4. Proposed mechanism of the aminocarbonylation of nitroalkenes with carbamoylsilanes

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