可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成反应

引用本文: 代雪梅, 李延军, 张少南, 龚磊. 可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成反应[J]. 有机化学, 2019, 39(6): 1711-1719. doi: 10.6023/cjoc201902022 shu

Citation: Dai Xuemei, Li Yanjun, Zhang Shaonan, Gong Lei. Visible-Light-Induced[3+2] Annulation of Cyclopropylamines with 1, 2-Diketone Derivatives[J]. Chinese Journal of Organic Chemistry, 2019, 39(6): 1711-1719. doi: 10.6023/cjoc201902022 shu

可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成反应

福建省化学生物学重点实验室能源材料化学协同创新中心厦门大学化学化工学院厦门 361005

通讯作者: 龚磊, gongl@xmu.edu.cn

基金项目:

国家自然科学基金（No.21572184）、福建省自然科学基金（No.2017J06006）、中央高校基本科研业务费（No.20720160027）资助项目

摘要: 报道了一种可见光催化环丙基胺与1，2-二芳基乙二酮衍生物的[3+2]环加成反应，合成了一系列α-氨基呋喃衍生物，该反应条件温和，产率良好，操作简单.这一方法为潜在生物活性分子骨架α-氨基呋喃衍生物的合成提供了一条高效便捷的路径.

关键词:

English

Visible-Light-Induced[3+2] Annulation of Cyclopropylamines with 1, 2-Diketone Derivatives

Key Laboratory of Chemical Biology of Fujian Province, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Corresponding author: Gong Lei, E-mail: gongl@xmu.edu.cn

Received Date: 21 February 2019
Revised Date: 27 March 2019
Available Online: 25 June 2019
Fund Project:

Project supported by the National Natural Science Foundation of China (No. 21572184), the Natural Science Foundation of Fujian Province (No. 2017J06006), and the Fundamental Research Funds for the Central Universities (No. 20720160027)

Abstract: A visible-light-induced[3+2] annulation of arylcyclopropylamines and 1, 2-diarylethanediones was report. A series of α-amino tetrahydrofuran derivatives were synthesized in moderate to good isolated yields under mild reaction conditions. This method would provide an efficient and convenient approach to α-amino tetrahydrofurans which are potentially important buiding blocks in bioactive compounds.

Key words:

α-氨基氧杂五、六元环在许多药物分子和生物活性分子中广泛存在^[1], 如丝裂霉素^[2]是一种抗肿瘤药物, 而许多核苷分子和糖脂分子含有α-氨基氧杂六元环基本结构^[3] (Scheme 1a).因此, 发展高效、便捷的方法制备α-氨基含氧杂环是具有重要意义的研究方向.其中, α-氨基呋喃衍生物的合成方法非常有限, 通常是通过相应卤代物或醇的亲核取代或不饱和氧杂五元环的氢胺基化来进行, 然而, 这些方法大多条件苛刻、操作繁琐, 在实际应用中受到了较大的限制^{[1, 4]}.

图式 1

图式 1. 可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成

Scheme 1. [3+2] cycloaddition of cyclopropylamines and 1, 2-diketone derivatives

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近年来, 可见光催化因反应温和、易于操作等优点在有机合成中取得了广泛的应用^{[5, 6]}.在可见光氧化还原中, 胺类物质往往充当着电子给体的角色, 因此在光催化循环中胺往往被单电子氧化成氮自由基正离子, 在不同的条件下发生不同的反应.氮自由基正离子可以进一步失去质子形成亲核性的α-氨基烷基自由基, 接着再与不饱和碳碳键发生自由基加成^[7]; α-氨基烷基自由基还可以再失去1个电子形成亚胺正离子, 从而参与后续的反应^[8]; 若氮的α位被环丙基取代, 氮自由基正离子开环得到β-碳自由基亚胺正离子, 然后发生后续反应^[9].

本工作选择了环丙基胺和1, 2-二酮衍生物作为反应底物, 在可见光催化下经自由基开环进而发生[3+2]环加成反应(Scheme 1b).条件温和, 原子经济性好, 操作简单, 产率良好, 具有一定的底物适用性.首次在可见光条件下实现了环丙基胺与碳杂原子不饱和键的自由基加成, 一步构建α-氨基呋喃衍生物, 为这类潜在生物活性分子骨架提供了一条高效便捷的合成路径.

1. 结果与讨论

在最初的研究中, 我们选择了1, 2-二苯基乙二酮(1a)和N-苯基环丙基胺(2a)作为模型底物、Ru(bpy)₃(PF₆)₂作为可见光催化剂, 在24 W蓝光LED灯照射12 h对反应条件进行了系统筛选(表 1).如Entries 1~8所示, 溶剂对反应产率有着极大的影响:在氯仿(Entry 1)、四氢呋喃(THF) (Entry 2)、二氯甲烷(Entry 4)、N, N-二甲基甲酰胺(DMF) (Entry 6)、甲苯(Entry 7)及二甲基亚砜(DMSO) (Entry 8)中仅能观测到痕量的产物生成, 而在甲醇(Entry 3)和乙腈(Entry 5)中, 则分别以80%和53%的产率得到产物3a.然后, 我们以甲醇为溶剂, 考察了可见光催化剂对反应的影响(Entries 9~12), 结果表明, Ru(bpy)₃(PF₆)₂展现了最佳催化效果, 而使用同样载量的其它铱、钌可见光催化剂, 如[Ir(ppy)₂(dtbbpy)][PF₆] (Entry 9)、fac-Ir(ppy)₃(Entry 10)、Ru(bpz)₃[PF₆]₂ (Entry 11)则给出较低的产率, 使用有机可见光催化剂Mes- Acr⁺时反应基本无法进行(Entry 12).光源的筛选实验表明:用24 W白光CFL灯代替蓝光LED灯照射使得反应产率有一定程度的下降(61%, Entry 13), 用15 W紫外灯作为光源时则没有观察到3a的形成(Entry 14), 而在无光照时反应也无法进行(Entry 15).

表 1

表 1 反应条件优化^a

Table 1. Optimization of reaction conditions

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Entry	PC	Light source	Solvent	Additives	Time/h	yield^b
1	Ru(bpy)₃[PF₆]₂	Blue LEDs	CHCl₃	None	12	Trace
2	Ru(bpy)₃[PF₆]₂	Blue LEDs	THF	None	12	0
3	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	None	12	80
4	Ru(bpy)₃[PF₆]₂	Blue LEDs	DCM	None	12	Trace
5	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃CN	None	12	53
6	Ru(bpy)₃[PF₆]₂	Blue LEDs	DMF	None	12	Trace
7	Ru(bpy)₃[PF₆]₂	Blue LEDs	Toluene	None	12	Trace
8	Ru(bpy)₃[PF₆]₂	Blue LEDs	DMSO	None	12	Trace
9	[Ir(ppy)₂(dtbbpy)][PF₆]	Blue LEDs	CH₃OH	None	12	37
10	fac-Ir(ppy)₃	Blue LEDs	CH₃OH	None	12	12
11	Ru(bpz)₃[PF₆]₂	Blue LEDs	CH₃OH	None	12	7
12	Mes-Acr⁺	Blue LEDs	CH₃OH	None	12	4
13	Ru(bpy)₃[PF₆]₂	White CFL	CH₃OH	None	12	61
14	Ru(bpy)₃[PF₆]₂	UV lamps	CH₃OH	None	12	0
15	Ru(bpy)₃[PF₆]₂	None	CH₃OH	None	12	0
16	None	Blue LEDs	CH₃OH	None	12	27
17	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	Air	12	54
18	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	TEMPO	12	0
^a Reaction conditions: 1a (0.10 mmol), 2a (0.30 mmol), solvent (1.0 mL), indicated light source, under argon. ^b Determined by ¹H NMR analysis using 1, 3, 5-trimethoxybenzene as the internal standard. THF=tetrahydrofuran; DCM=dichloromethane; DMF=dimethylformamide; DMSO=dimethyl sulfoxide; TEMPO=2, 2, 6, 6-tetramethylpiperidinooxy; dtbbpy=4, 4'-di-tert-butyl-2, 2'-dipyridyl; ppy=(2-pyridinyl)phenyl; bpz=2, 2'-bipyrazine.

值得一提的是, 在不加入可见光催化剂时进行光照反应仍可进行, 但产率较低(27%, Entry 16).紫外可见吸收(UV-Vis)分析表明: 1, 2-二苯基乙二酮在蓝光区域有一定程度的吸收, 可能作为光敏性物质参与背景反应, 但效率不高.此外, 该反应在空气下仍能发生, 以54%的产率生成产物3a (Entry 17), 但5 equiv.自由基抑制剂四甲基哌啶氧化物(TEMPO)的加入则使反应无法进行(Entry 18).

根据以上结果, 确定了该反应的最佳反应条件为:氩气和室温条件下, 2 mol% Ru(bpy)₃(PF₆)₂作为可见光催化剂, 甲醇作为溶剂, 24 W蓝光LED灯为光源.

在最佳反应条件下, 对底物适用性进行了研究.如表 2所示, 1, 2-二芳基乙二酮底物对于芳环取代基具有良好的兼容性, 底物芳基含吸电子基团溴、氟、氯时, 产率为61~85% (产物3b~3e), 卤素官能团的兼容也为产物的进一步转化提供了更多机会.值得一提的是, 邻位氯代底物给出最高产率85%(产物3e), 产物结构也得到了单晶衍射的进一步证明.此外, 富电子底物同样适用于该反应, 如甲基、叔丁基、甲氧基取代1, 2-二芳基乙二酮均能以良好的分离产率(63%~75%)得到相应产物(3f~3i).遗憾的是, 1-苯基-1, 2-丙二酮和2, 3-丁二酮并不适用, 没有得到相应产物(3j, 3k).

表 2

表 2 1, 2-二酮衍生物底物范围

Table 2. Reaction scope of the 1, 2-diketones derivatives

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表 3展示了芳基环丙基胺底物范围:苯环邻、间、对位被甲基或甲氧基取代的芳基环丙基胺均适用于该反应, 以良好的分离产率(55%~74%)获得相应产物(3l~3q), 对位吸电子取代基(Cl, Br)产率相对较低, 以63%、35%的分离产率获得产物(3r, 3s).此外, 以上反应均存在非对映异构体, 产物dr值从1:1到2.5:1不等.我们认为较低的非对映选择性与呋喃产物α-位较小的空间位阻差异相关(芳基与芳酰基).

表 3

表 3 环丙基胺底物范围

Table 3. Reaction scope of the cyclopropylamines

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对反应机理进行了初步的验证, 如Scheme 2所示.在1a+2a→3a标准条件的反应中加入5 equiv. TEMPO, 产物3a未生成, 但高分辨质谱成功检测到了开环自由基与TEMPO的加合产物4 [HRMS (ESI) calcd for C₁₈H₂₉N₂O (M+H)⁺: 289.2274, found 289.2273] (Scheme 4a); 而加入5 equiv. 2-苯磺酰甲基丙烯酸乙酯作为自由基捕获剂, 产物3a同样未生成, 但检测到了开环自由基与2-苯磺酰甲基丙烯酸乙酯的自由基加成产物5 [HRMS (ESI) calcd for C₁₅H₁₉NO₂Na (M+H)⁺: 268.1308; found 268.1309] (Scheme 2b).以上实验充分证明了反应的自由基历程及开环自由基的存在.

图式 2

图式 2. 自由基捕获实验

Scheme 2. Radical trapping experiments

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根据上述结果和前人工作^{[9a, 10, 11]}, 我们对反应机理进行了推测, 认为这一[3+2]环加成反应是通过自由基加成(Scheme 3a)和自由基偶联(Scheme 3b)两种路径来进行的.

图式 3

图式 3. 可能的反应机理

Scheme 3. A proposed reaction mechanis

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一种路径为自由基加成机理(Scheme 3a).以1a和2a的反应为例, 催化剂Ru^Ⅱ经可见光照射后跃迁到激发态[Ru^Ⅱ]^*, 再被环丙基胺2a还原猝灭, 生成还原态的光催化剂Ru^Ⅰ, 同时2a被单电子氧化成氮自由基正离子A; A自发开环形成β-碳自由基亚胺正离子B; B再对1a中的碳氧双键加成, 生成σ-碳自由基亚胺正离子C; C发生分子内关环形成亚胺自由基正离子D, 进而被还原态的光催化剂Ru^Ⅰ单电子还原, 生成[3+2]加成产物3a, 而Ru^Ⅰ被单电子氧化成催化剂Ru^Ⅱ, 完成光催化循环.

另一种路径为自由基偶联机理(Scheme 3b). 2a被激发态的光催化剂[Ru^Ⅱ]^*单电子氧化成氮自由基正离子A, 同时激发态光催化剂被单电子还原成Ru^Ⅰ; A自发开环形成β-碳自由基亚胺正离子B; 1a与Ru^Ⅰ发生单电子转移, 生成自由基负离子E.根据文献报道: [E_1/2^rex(1a)=-0.92 V^[10]; E_1/2^Ⅱ/Ⅰ(Ru)=-1.33 V^[11]], 表明Ru^Ⅰ对1a的单电子还原是热力学有利的过程; 最后, E和B发生自由基偶联得到产物3a.

我们认为在该反应中两种机理都有可能存在, 是相互竞争的.

2. 结论

本工作发展了可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成反应, 首次在可见光条件下实现了环丙基胺与碳杂原子不饱和键的自由基加成, 并一步构建α-氨基呋喃衍生物, 条件温和, 操作简单, 产率良好.反应具有高原子经济性和一定的底物适用性, 为潜在生物活性分子α-氨基呋喃衍生物提供了一条高效便捷的合成路径.

3. 实验部分

3.1 仪器与试剂

1, 2-二芳基乙二酮衍生物1g^[12]和N-芳基环丙基胺2a~2i^[13]根据相应的参考文献合成得到, 其余试剂均从商业渠道上购买得到(TCI, Aldrich, Energy, Alfa, Adamas-beta^® and J & K), 未经纯化直接使用. ¹H NMR及¹³C NMR在Bruker AM (400 MHz), Bruker AM (500 MHz), Bruker AM (850 MHz)测得, 样品溶于氘代氯仿于常温下测试, TMS为内标.使用NMR标准如下: CDCl₃ δ 7.26 (¹H NMR), 77.2 (¹³C NMR); (CD₃)₂CO δ 2.05 (¹H NMR), 29.7, 206.4 (¹³C NMR); IR光谱在NicoletAvatar 330 FT-IR型红外光谱仪上测得; 高分辨质谱在Bruker En Apex Ultra 7.0 T FT-MS仪器上测得; UV-Vis吸收光谱在10.0 mm的石英比色皿中用Shimadzu UV-2550测得.

3.2 实验方法

在带有搅拌子干燥的10 mL Schlenk管中加入1 (0.20 mmol)、2 (0.60 mmol)、Ru(bpy)₃(PF₆)₂ (0.004 mmol)和2.0 mL甲醇, 冻抽三次换氩气.恢复至室温, 置于24 W蓝光LED灯约3 cm处, 在恒温柜(25 ℃)中反应.通过薄层色谱(TLC)检测1消失, 脱溶, 经柱色谱分离得到相应的产物, 洗脱剂: V(石油醚):V(乙酸乙酯):V(三乙胺)=100:10:1.

苯基-(2-苯基-5-苯胺基四氢呋喃-2-基)甲酮(3a):无色油状液体, 46.0 mg, 产率67%. dr=1.1:1. ¹H NMR (500 MHz, CDCl₃) δ: 8.00~8.08 (m, 1H), 7.84~7.90 (m, 1H), 7.51 (d, J=8.5 Hz, 2H), 7.15~7.34 (m, 6H), 7.02~7.07 (m, 2H), 6.67~6.85 (m, 2H), 6.59 (d, J=7.5 Hz, 1H), 5.42~5.83 (m, 1H), 4.46 (d, J=9.1 Hz, 0.52H), 4.01 (d, J=8.5 Hz, 0.48H), 3.17~3.49 (m, 1H), 2.22~2.48 (m, 1H), 1.88~2.18 (m, 1H), 1.74~1.83 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 200.4, 199.3, 145.9, 145.7, 142.9, 142.3, 134.7, 132.7, 132.1, 131.0, 130.8, 129.4, 129.0, 128.8, 128.7, 128.1, 127.7, 127.6, 127.5, 124.8, 124.5, 119.2, 119.0, 114.6, 114.5, 92.6, 91.9, 87.7, 87.0, 37.3, 36.7, 33.0, 32.0; IR (film) ν: 3057, 2922, 1676, 1604, 1507, 1259, 1033, 752, 700 cm^-1. HRMS (ESI) calcd for C₂₃H₂₁NO₂Na (M+Na)⁺: 366.1465, found 366.1457.

(4-溴苯基)-(2-(4-溴苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3b):无色油状液体, 61.1 mg, 产率61%. dr=1.2:1. ¹H NMR (500 MHz, CDCl₃) δ: 7.90 (d, J=8.6 Hz, 1H), 7.69 (d, J=8.6 Hz, 1H), 7.46 (dd, J=8.7, 2.3 Hz, 2H), 7.33~7.42 (m, 3H), 7.23 (t, J=7.9 Hz, 1H), 7.17 (d, J=8.7 Hz, 1H), 7.03~7.10 (m, 1H), 6.66~6.89 (m, 2H), 6.52~6.60 (m, 1H), 5.47~5.83 (m, 1H), 4.46 (d, J=9.0 Hz, 0.45H), 4.00 (d, J=8.1 Hz, 0.55H), 3.16~3.48 (m, 1H), 2.25~2.49 (m, 1H), 1.85~2.17 (m, 1H), 1.74~1.85 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 199.2, 197.7, 145.6, 145.3, 141.8, 140.9, 133.1 (2), 132.5, 132.2, 132.1, 132.0, 131.5, 131.1, 129.6, 129.1, 128.3, 127.6, 126.6, 126.2, 121.9, 121.8, 119.5, 119.3, 114.4 (2), 92.2, 91.4, 87.6, 87.4, 37.1, 36.6, 32.9, 31.9; IR (film) ν: 3408, 2923, 1676, 1604, 1485, 1257, 1008, 819, 750 cm^-1. HRMS (ESI) calcd for C₂₃H₁₉Br₂NO₂Na (M+Na)⁺: 521.9675, found 521.9675.

(4-氟苯基)-(2-(4-氟苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3c):无色油状液体, 53.1 mg, 产率70%. dr=1.2:1. ¹H NMR (500 MHz, CDCl₃) δ: 8.05~8.16 (m, 1H), 7.86~7.95 (m, 5.7 Hz, 1H), 7.43~7.51 (m, 2H), 7.23 (t, J=7.8 Hz, 1H), 6.93~7.10 (m, 4H), 6.67~6.80 (m, 3H), 6.59 (d, J=7.9 Hz, 1H), 5.45~5.90 (m, 1H), 4.49 (d, J=9.0 Hz, 0.45H), 4.03 (d, J=8.3 Hz, 0.55H), 3.17~3.51 (m, 1H), 2.26~2.51 (m, 1H), 1.86~2.19 (m, 1H), 1.72~1.86 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 198.8, 197.4, 166.5, 166.1, 164.5, 164.1, 163.3 (2), 161.3 (2), 145.7, 145.4, 138.6, 138.5, 137.8 (2), 133.8 (2), 133.5, 133.4, 130.8 (4), 129.5, 129.4, 129.0, 126.6, 126.5, 126.2 (2), 119.4, 119.2, 115.9, 115.8, 115.7, 115.6, 115.3, 115.2 (2), 114.9, 114.7, 114.4 (2), 92.2, 91.4, 87.5, 87.2, 37.3, 36.8, 32.9, 31.9; IR (film) ν: 3403, 2925, 1671, 1603, 1507, 1234, 1156, 836, 752 cm^-1. HRMS (ESI) calcd for C₂₃H₁₉F₂NO₂Na (M+Na)⁺: 402.1276, found 402.1267.

(4-氯苯基)-(2-(4-氯苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3d):无色油状液体, 50.3 mg, 产率61%. dr=1.2:1. ¹H NMR (500 MHz, CDCl₃) δ: 7.99 (d, J=8.7 Hz, 1H), 7.79 (d, J=8.7 Hz, 1H), 7.43 (t, J=8.2 Hz, 2H), 7.27~7.33 (m, 2H), 7.21~7.26 (m, 2H), 7.04~7.09 (m, 1H), 6.99~7.04 (m, 1H), 6.67~6.90 (m, 2H), 6.57 (d, J=7.3 Hz, 1H), 5.48~5.83 (m, 1H), 4.47 (d, J=9.0 Hz, 0.45H), 4.01 (d, J=8.2 Hz, 0.54H), 3.15~3.50 (m, 1H), 2.27~2.49 (m, 1H), 1.86~2.17 (m, 1H), 1.75~1.84 (m, 1H). ¹³C NMR (126 MHz, CDCl₃) δ: 199.1, 197.5, 145.6, 145.3, 141.3, 140.4, 139.4, 138.7, 133.7(2), 132.7, 132.7, 132.4, 132.1, 129.6, 129.1(2), 129.0, 128.5, 128.1, 126.3, 125.9, 119.5, 119.3, 114.4(2), 92.2, 91.4, 87.6, 87.4, 37.2, 36.7, 32.9, 31.9; IR (film) ν: 3404, 2924, 1677, 1604, 1506, 1258, 1091, 823, 751 cm^-1. HRMS (ESI) calcd for C₂₃H₁₉Cl₂NO₂Na (M+Na)⁺: 434.0685, found 434.0682.

(2-氯苯基)-(2-(2-氯苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3e):白色固体, 70.1 mg, 产率85%. dr=1.2:1. ¹H NMR (400 MHz, CDCl₃) δ: 7.76~7.90 (m, 1H), 7.07~7.42 (m, 8H), 6.72~7.00 (m, 4H), 5.87 (s, 0.44H), 5.72 (s, 0.56H), 4.43 (s, 1H), 3.55~3.72 (m, 1H), 2.32~2.64 (m, 1H), 1.78~2.25 (m, 2H); ¹³C NMR (214 MHz, CDCl₃) δ: 196.9, 195.4, 145.7, 145.6, 141.3, 140.8, 135.4, 135.3, 133.4, 133.0, 131.6, 131.3 (2), 131.2, 131.1, 131.0, 130.4, 130.3, 130.1, 130.0, 129.6, 129.4, 129.1, 129.0, 127.9, 127.1 (2), 126.9, 125.4, 125.4, 119.4, 114.8, 114.4, 90.3, 90.1, 88.6, 87.9, 34.1, 33.2, 32.9, 32.5; IR (film) ν: 3410, 1701, 1637, 1604, 1508, 1432, 1011, 748, 693 cm^-1. HRMS (ESI) calcd for C₂₃H₁₉Cl₂NO₂Na (M+Na)⁺: 434.0685, found 434.0682.

(4-甲基苯基)-(2-(4-甲基苯基)-5-苯胺基四氢呋喃- 2-基)甲酮(3f):无色油状液体, 49.0 mg, 产率66%. dr=1.1:1. ¹H NMR (500 MHz, CDCl₃) δ: 8.00 (d, J=8.3 Hz, 1H), 7.83 (d, J=8.3 Hz, 1H), 7.41 (dd, J=8.3, 2.1 Hz, 2H), 7.19~7.24 (m, 1H), 7.05~7.16 (m, 4H), 6.70~6.91 (m, 3H), 6.62 (d, J=7.2 Hz, 1H), 5.45~5.86 (m, 1H), 4.47 (d, J=9.1 Hz, 0.53H), 4.02 (d, J=8.7 Hz, 0.47H), 3.18~3.48 (m, 1H), 2.18~2.47 (m, 7H), 1.90~2.17 (m, 1H), 1.74~1.84 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 200.0, 198.8, 145.9, 145.8, 143.4, 142.8, 140.2, 139.6, 137.1, 132.2, 132.1, 131.2, 131.0, 129.5, 129.4 (2), 128.9, 128.8, 128.4, 124.8, 124.4, 119.2, 118.9, 114.7, 114.5, 92.6, 92.0, 87.5, 86.9, 37.3, 36.6, 33.0, 32.0, 21.8, 21.6, 21.2(2); IR (film) ν: 3441, 2919, 1665, 1605, 1509, 1261, 1180, 750, 693 cm^-1. HRMS (ESI) calcd for C₂₅H₂₅NO₂Na (M+Na)⁺: 394.1778, found 394.1767.

(4-叔丁基苯基)-(2-(4-叔丁基苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3g):无色油状液体, 57.4 mg, 产率63%. dr=2.5:1. ¹H NMR (400 MHz, CDCl₃) δ: 7.75~8.10 (m, 2H), 7.16~7.50 (m, 5H), 6.98~7.12 (m, 3H), 6.65~6.97 (m, 2H), 6.52~6.57 (m, 1H), 5.43~5.82 (m, 1H), 4.44 (d, J=9.2 Hz, 0.30H), 3.95 (d, J=8.6 Hz, 0.70H), 3.14~3.51 (m, 1H), 2.20~2.48 (m, 1H), 1.88~2.20 (m, 1H), 1.70~1.84 (m, 1H), 1.15~1.37 (m, 18H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.7, 199.3, 156.3, 155.6, 150.3 (2), 146.0, 145.7, 139.8, 139.2, 132.1(2), 131.1, 130.8, 129.5, 129.4, 128.9, 125.7, 125.6, 125.0, 124.6, 124.5, 124.3, 121.2, 119.1, 118.9, 118.0, 114.6, 92.7, 92.0, 87.2, 86.7, 37.4, 36.7, 35.2, 35.0, 34.6, 34.6, 33.0, 32.0, 31.5 (2), 31.2 (2); IR (film) ν: 3400, 2962, 1671, 1604, 1506, 1267, 1190, 749, 692 cm^-1. HRMS (ESI) calcd for C₃₁H₃₇NO₂Na (M+Na)⁺: 478.2717, found 478.2714.

(4-甲氧基苯基)-(2-(4-甲氧基苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3h):无色油状液体, 59.7 mg, 产率74%. dr=1.1:1. ¹H NMR (500 MHz, CDCl₃) δ: 8.10 (d, J=9.0 Hz, 1H), 7.94 (d, J=9.0 Hz, 1H), 7.43 (dd, J=8.8, 2.1 Hz, 2H), 7.19~7.24 (m, 1H), 7.05~7.10 (m, 1H), 6.76~6.88 (m, 5H), 6.58 (dd, J=29.3, 8.2 Hz, 2H), 5.45~5.90 (m, 1H), 4.48 (d, J=9.0 Hz, 0.53H), 4.03 (d, J=8.8 Hz, 0.47H), 3.67~3.82 (m, 6H), 3.14~3.47 (m, 1H), 2.24~2.49 (m, 1H), 1.86~2.17 (m, 1H), 1.73~1.83 (m, 1H). ¹³C NMR (126 MHz, CDCl₃) δ: 199.1, 197.8, 163.1, 162.7, 159.0 (2), 146.0, 145.8, 135.3, 134.7, 133.5, 133.3, 129.4, 129.0, 127.6, 127.5, 126.1, 125.7, 119.2, 118.9, 114.7, 114.5, 114.1, 114.0, 113.3, 112.9, 92.4, 91.8, 87.3, 86.8, 55.5, 55.4, 55.3 (2), 37.4, 36.6, 33.0, 32.0; IR (film) ν: 3395, 2933, 1665, 1602, 1509, 1254, 1172, 834, 753 cm^-1. HRMS (ESI) calcd for C₂₅H₂₅NO₄Na (M+Na)⁺: 426.1676, found 426.1670.

(3-甲氧基苯基)-(2-(3-甲氧基苯基)-5-苯胺基四氢呋喃-2-基)甲酮(3i):无色油状液体, 60.5 mg, 产率75%. dr=1.1:1. ¹H NMR (500 MHz, CDCl₃) δ: 7.62~7.68 (m, 1H), 7.46~7.52 (m, 1H), 7.14~7.25 (m, 3H), 6.97~7.11 (m, 4H), 6.69~6.86 (m, 3H), 6.60~6.65 (m, 1H), 5.52~5.83 (m, 1H), 4.47 (d, J=8.9 Hz, 0.52H), 4.05 (d, J=8.5 Hz, 0.47H), 3.75 (d, J=40.6 Hz, 3H), 3.57 (d, J=7.8 Hz, 3H), 3.23~3.48 (m, 1H), 2.24~2.49 (m, 1H), 1.91~2.21 (m, 1H), 1.75~1.87 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 199.9, 198.1, 160.1, 159.2, 158.8, 145.8, 145.7, 144.9, 144.0, 136.0, 135.8, 129.9, 129.8, 129.4, 129.0 (2), 128.7, 123.7, 123.4, 119.9, 119.3, 119.2, 119.1, 117.0, 116.8, 114.9, 114.8, 114.6, 114.5, 113.5, 112.7, 110.3, 109.7, 92.7, 91.8, 87.6, 87.0, 55.4, 55.4, 55.2, 55.1, 37.2, 36.6, 32.9, 32.1; IR (film) ν: 3407, 2924, 1672, 1604, 1487, 1266, 1183, 750, 696 cm^-1. HRMS (ESI) calcd for C₂₅H₂₅NO₄Na (M+Na)⁺: 426.1676, found 426.1673.

苯基(2-苯基-5-(邻甲苯基胺基)四氢呋喃-2-基)甲酮(3l):无色油状液体, 40.7 mg, 产率57%. dr=1:1. ¹H NMR (400 MHz, CDCl₃) δ: 7.97~8.09 (m, 1H), 7.81~7.92 (m, 1H), 6.95~7.60 (m, 10H), 6.56~6.89 (m, 2H), 5.46~5.88 (m, 1H), 4.26 (d, J=9.2 Hz, 0.50H), 3.83 (d, J=8.3 Hz, 0.51H), 3.18~3.54 (m, 1H), 1.66~2.59 (m, 6H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.5, 199.4, 143.9, 143.6, 142.9, 142.2, 134.7, 134.6, 132.8, 132.2, 131.1, 130.7, 130.4, 130.0, 128.8, 128.7, 128.1, 127.6, 127.6, 127.3, 126.9, 124.8, 124.5, 122.8, 122.7, 119.0, 118.7, 112.9, 112.8, 92.6, 92.1, 87.3, 86.8, 37.5, 36.8, 33.2, 32.1, 17.7, 17.3; IR (film) ν: 3422, 2922, 1675, 1607, 1448, 1260, 1050, 863, 753 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₂Na (M+Na)⁺: 380.1621, found 380.1618.

苯基(2-苯基-5-(间甲苯基胺基)四氢呋喃-2-基)甲酮(3m):无色油状液体, 46.5 mg, 产率65%. dr=1.1:1. ¹H NMR (400 MHz, CDCl₃) δ: 8.04~8.15 (m, 1H), 7.84~7. 95 (m, 1H), 7.50~7.58 (m, 2H), 7. 19~7.48 (m, 5H), 6.92~7.13 (m, 2H), 6.32~6.70 (m, 3H), 5.42~5.83 (m, 1H), 4.44 (d, J=9.2 Hz, 0.47H), 3.95 (d, J=8.5 Hz, 0.53H), 3.14~3.54 (m, 1H), 2.27~2.47 (m, 1H), 2.22 (d, J=19.1 Hz, 3H), 1.91~2.17 (m, 1H), 1.73~1.85 (m, 1H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.4, 199.3, 145.7, 145.5, 142.7, 142.3, 139.1, 138.5, 134.6, 134.6, 132.6, 132.0, 130.9, 130.7, 129.1, 128.7, 128.7, 128.6, 127.9, 127.5, 127.4, 124.7, 124.3, 120.0, 119.8, 115.4, 115.0, 111.6 (2), 92.3, 91.7, 87.7, 86.8, 37.2, 36.5, 32.8, 31.8, 21.6, 21.5; IR (film) ν: 3400, 2921, 1676, 1608, 1490, 1261, 1180, 859, 757 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₂Na (M+ Na)⁺: 380.1621, found 380.1617.

苯基(2-苯基-5-(对甲苯基胺基)四氢呋喃-2-基)甲酮(3n):无色油状液体, 40.0 mg, 产率56%. dr=1:1. ¹H NMR (400 MHz, CDCl₃) δ: 8.02~8.06 (m, 1H), 7.86~7.91 (m, 1H), 7.49~7.53 (m, 2H), 7.18~7.34 (m, 5H), 7.04~7.10 (m, 1H), 6.97~7.02 (m, 1H), 6.84~6.89 (m, 1H), 6.62~6.68 (m, 1H), 6.49~6.54 (m, 1H), 5.41~5.80 (m, 1H), 4.34 (d, J=9.4 Hz, 0.51H), 3.88 (d, J=8.9 Hz, 0.49H), 3.18~3.46 (m, 1H), 2.19~2.45 (m, 4H), 1.90~2.17 (m, 1H), 1.70~1.83 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 200.3, 199.4, 143.5, 143.4, 143.0, 142.5, 134.8, 134.7, 132.7, 132.1, 131.0, 130.9, 129.9, 129.5, 128.8, 128.7, 128.5, 128.3, 128.0, 127.7, 127.5, 124.8, 124.5, 114.9, 114.6, 92.5, 91.9, 88.4, 87.3, 37.4, 36.7, 33.0, 31.9, 20.6 (2); IR (film) ν: 3405, 2918, 1674, 1616, 1519, 1260, 1181, 810, 756 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₂Na (M+Na)⁺: 380.1621, found 380.1621.

苯基(2-苯基-5-(对甲氧基苯基胺基)四氢呋喃-2-基)甲酮(3o):无色油状液体, 41.1 mg, 产率55%. dr=1.1:1. ¹H NMR (850 MHz, CDCl₃) δ: 8.03~8.09 (m, 1H), 7.86~7.94 (m, 1H), 7.42~7.54 (m, 2H), 7.28~7.32 (m, 2H), 7.16~7.28 (m, 3H), 7.08~7.12 (m, 1H), 7.01 (d, J=8.1 Hz, 1H), 6.88 (d, J=8.0 Hz, 1H), 6.65~6.70 (m, 1H), 6.48~6.58 (m, 1H), 5.42~5.82 (m, 1H), 4.37 (s, 0.52H), 3.90 (s, 0.47H), 3.19~3.47 (m, 1H), 2.30~2.43 (m, 1H), 2.25 (d, J=59.1 Hz, 3H), 1.93~2.18 (m, 1H), 1.72~1.85 (m, 1H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.3, 199.4, 143.5, 143.4, 143.0, 142.5, 134.8, 134.7, 132.7, 132.2, 131.0, 130.9, 129.9, 129.5, 128.8, 128.7, 128.5, 128.3, 128.0, 127.8, 127.5, 124.8, 124.5, 114.9, 114.6, 92.5, 91.9, 88.3, 87.3, 37.4, 36.7, 33.0, 31.9, 20.7, 20.6; IR (film) ν: 3405, 2918, 1674, 1616, 1519, 1260, 1181, 810, 756 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₃Na (M+Na)⁺: 396.1570, found 396.1578.

苯基(2-苯基-5-(邻甲氧基苯基胺基)四氢呋喃-2-基)甲酮(3p):无色油状液体, 47.8 mg, 产率64%. dr=1.1:1. ¹H NMR (400 MHz, CDCl₃) δ: 8.03~8.12 (m, 1H), 7.81~7.92 (m, 1H), 7.44~7.57 (m, 2H), 7.15~7.38 (m, 5H), 6.74~7.09 (m, 4H), 6.52~6.70 (m, 1H), 5.44~5.87 (m, 1H), 5.02 (d, J=8.8 Hz, 0.52H), 4.61 (d, J=8.3 Hz, 0.49H), 3.76 (d, J=105.4 Hz, 3H), 3.20~3.56 (m, 1H), 1.88~2.52 (m, 3H); ¹³C NMR (151 MHz, CDCl₃) δ: 200.5, 199.4, 147.1, 146.9, 142.9, 142.3, 135.8, 135.4, 134.7 (2), 132.7, 131.9, 131.1, 130.7, 128.8, 128.7, 128.1, 127.5 (2), 127.4, 124.9, 124.5, 121.5, 121.0, 118.5, 118.2, 112.7, 112.5, 109.9, 109.5, 92.6, 92.0, 87.0, 86.7, 55.6, 55.3, 37.4, 36.8, 32.9, 32.0; IR (film) ν: 3423, 2924, 1676, 1601, 1513, 1224, 1180, 1027, 701 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₃Na (M+Na)⁺: 396.1570, found 396.1566.

苯基(2-苯基-5-(间甲氧基苯基胺基)四氢呋喃-2-基)甲酮(3q):无色油状液体, 55.3 mg, 产率74%. dr=1:1. ¹H NMR (400 MHz, CDCl₃) δ: 8.01~8.08 (m, 1H), 7.85~7.91 (m, 1H), 7.48~7.55 (m, 2H), 7.16~7.44 (m, 5H), 6.90~7.13 (m, 2H), 6.13~6.42 (m, 3H), 5.44~5.82 (m, 1H), 4.50 (d, J=8.9 Hz, 0.48H), 4.04 (d, J=8.3 Hz, 0.49H), 3.69 (d, J=9.2 Hz, 3H), 3.18~3.48 (m, 1H), 2.22~2.45 (m, 1H), 1.89~2.19 (m, 1H), 1.71~1.85 (m, 1H); ¹³C NMR (126 MHz, CDCl₃) δ: 200.4, 199.1, 160.9, 160.5, 147.3, 147.1, 142.9, 142.3, 134.7, 134.7, 132.7, 132.1, 131.0, 130.8, 130.2, 129.7, 128.8, 128.7, 128.0, 127.7, 127.5, 124.8, 124.5, 107.5, 107.3, 105.0, 104.3, 100.6, 100.2, 92.7, 91.9, 87.6, 87.0, 55.2, 55.2, 37.3, 36.7, 32.9, 32.0; IR (film) ν: 3397, 2933, 1676, 1600, 1494, 1211, 1162, 758, 702 cm^-1. HRMS (ESI) calcd for C₂₄H₂₃NO₃Na (M+Na)⁺: 396.1570, found 396.1571.

苯基(2-苯基-5-(对氯苯基胺基)四氢呋喃-2-基)甲酮(3r):无色油状液体, 47.6 mg, 产率63%. dr=1:1. ¹H NMR (400 MHz, CDCl₃) δ: 7.98~8.04 (m, 1H), 7.80~7.84 (m, 1H), 7.46~7.51 (m, 2H), 7.20~7.33 (m, 5H), 7.10~7.14 (m, 1H), 7.03~7.07 (m, 1H), 6.93~6.97 (m, 1H), 6.61~6.68 (m, 1H), 6.45~6.50 (m, 1H), 5.38~5.73 (m, 1H), 4.46 (d, J=9.1 Hz, 0.49H), 4.01 (d, J=8.2 Hz, 0.50H), 3.22~3.47 (m, 1H), 2.24~2.48 (m, 1H), 1.93~2.13 (m, 1H), 1.74~1.82 (m, 1H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.5, 199.2, 144.4, 144.2, 142.7, 142.0, 134.6 (2), 132.8, 132.2, 131.0, 130.7, 129.3, 128.9, 128.8, 128.7, 128.1, 127.7 (2), 127.6, 124.7, 124.4, 124.0, 123.7, 115.6 (2), 92.6, 92.0, 87.4, 86.8, 37.2, 36.6, 32.9, 31.9; IR (film) ν: 3398, 2927, 1676, 1560, 1493, 1259, 1180, 818, 701 cm^-1. HRMS (ESI) calcd for C₂₃H₂₀ClNO₂Na (M+Na)⁺: 400.1075, found 400.1072.

苯基(2-苯基-5-(对溴苯基胺基)四氢呋喃-2-基)甲酮(3s):无色油状液体, 29.6 mg, 产率35%. dr=1.1:1. ¹H NMR (400 MHz, CDCl₃) δ: 7.98~8.06 (m, 1H), 7.82 (dd, J=8.4, 1.4 Hz, 1H), 7.43~7.53 (m, 2H), 7.20~7.35 (m, 6H), 7.04~7.12 (m, 2H), 6.58~6.64 (m, 1H), 6.42~6.46 (m, 1H), 5.38~5.76 (m, 1H), 4.49 (d, J=9.0 Hz, 0.47H), 4.03 (d, J=8.2 Hz, 0.53H), 3.23~3.48 (m, 1H), 2.24~2.49 (m, 1H), 1.94~2.14 (m, 1H), 1.76~1.84 (m, 1H); ¹³C NMR (214 MHz, CDCl₃) δ: 200.5, 199.1, 144.9, 144.7, 142.7, 142.0, 134.6 (2), 132.8, 132.2 (2), 131.6, 131.0, 130.7, 128.9, 128.8, 128.1, 127.8, 127.7, 127.6, 124.7, 124.4, 116.1 (2), 111.2, 110.9, 92.7, 92.0, 87.3, 86.7, 37.2, 36.6, 32.9, 31.9; IR (film) ν: 3406, 2925, 1674, 1595, 1489, 1292, 1179, 815, 701 cm^-1. HRMS (ESI) calcd for C₂₃H₂₀BrNO₂Na (M+Na)⁺: 444.0570, found 444.0569.

辅助材料(Supporting Information) 化合物3的¹H NMR和¹³C NMR谱图、紫外可见吸收光谱, 以及化合物3e的晶体数据.这些材料可以免费从本刊网站(http://sioc-journal.cn/)上下载.

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图式 1 可见光催化环丙基胺与1, 2-二酮衍生物的[3+2]环加成

Scheme 1 [3+2] cycloaddition of cyclopropylamines and 1, 2-diketone derivatives

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图式 2 自由基捕获实验

Scheme 2 Radical trapping experiments

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图式 3 可能的反应机理

Scheme 3 A proposed reaction mechanis

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表 1 反应条件优化^a

Table 1. Optimization of reaction conditions


Entry	PC	Light source	Solvent	Additives	Time/h	yield^b
1	Ru(bpy)₃[PF₆]₂	Blue LEDs	CHCl₃	None	12	Trace
2	Ru(bpy)₃[PF₆]₂	Blue LEDs	THF	None	12	0
3	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	None	12	80
4	Ru(bpy)₃[PF₆]₂	Blue LEDs	DCM	None	12	Trace
5	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃CN	None	12	53
6	Ru(bpy)₃[PF₆]₂	Blue LEDs	DMF	None	12	Trace
7	Ru(bpy)₃[PF₆]₂	Blue LEDs	Toluene	None	12	Trace
8	Ru(bpy)₃[PF₆]₂	Blue LEDs	DMSO	None	12	Trace
9	[Ir(ppy)₂(dtbbpy)][PF₆]	Blue LEDs	CH₃OH	None	12	37
10	fac-Ir(ppy)₃	Blue LEDs	CH₃OH	None	12	12
11	Ru(bpz)₃[PF₆]₂	Blue LEDs	CH₃OH	None	12	7
12	Mes-Acr⁺	Blue LEDs	CH₃OH	None	12	4
13	Ru(bpy)₃[PF₆]₂	White CFL	CH₃OH	None	12	61
14	Ru(bpy)₃[PF₆]₂	UV lamps	CH₃OH	None	12	0
15	Ru(bpy)₃[PF₆]₂	None	CH₃OH	None	12	0
16	None	Blue LEDs	CH₃OH	None	12	27
17	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	Air	12	54
18	Ru(bpy)₃[PF₆]₂	Blue LEDs	CH₃OH	TEMPO	12	0
^a Reaction conditions: 1a (0.10 mmol), 2a (0.30 mmol), solvent (1.0 mL), indicated light source, under argon. ^b Determined by ¹H NMR analysis using 1, 3, 5-trimethoxybenzene as the internal standard. THF=tetrahydrofuran; DCM=dichloromethane; DMF=dimethylformamide; DMSO=dimethyl sulfoxide; TEMPO=2, 2, 6, 6-tetramethylpiperidinooxy; dtbbpy=4, 4'-di-tert-butyl-2, 2'-dipyridyl; ppy=(2-pyridinyl)phenyl; bpz=2, 2'-bipyrazine.

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表 2 1, 2-二酮衍生物底物范围

Table 2. Reaction scope of the 1, 2-diketones derivatives

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表 3 环丙基胺底物范围

Table 3. Reaction scope of the cyclopropylamines

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