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2026 , Vol. 46 >Issue 2: 496 - 506

DOI: https://doi.org/10.6023/cjoc202507037

研究论文

铜催化3-硝基色烯与烯胺酮环化反应合成2H-色烯并吡咯衍生物

  • 梁婉婷 ,
  • 陈思怡 ,
  • 徐恩琪 ,
  • 陈雪冰 , *
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  • 红河学院化学与资源工程学院 云南省绿色食品中越双边国际联合实验室 云南蒙自 661199

收稿日期: 2025-07-28

  修回日期: 2025-09-25

  网络出版日期: 2025-11-05

基金资助

云南省绿色食品中越双边国际联合实验室(202403AP140032)

收起

Copper-Catalyzed Cyclization Reaction of 3-Nitrochromenes with Enaminones to Synthesize of 2H-Chromeno-pyrrole Derivatives

  • Wanting Liang ,
  • Siyi Chen ,
  • Enqi Xu ,
  • Xuebing Chen , *
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  • Yunnan Province International Joint Laboratory of Green Food (China-Vietnam), School of Chemistry and Resource Engineering, Honghe University, Mengzi, Yunnan 661199
*E-mail:

Received date: 2025-07-28

  Revised date: 2025-09-25

  Online published: 2025-11-05

Supported by

Yunnan Provincial International Joint Laboratory of Green Food (China-Vietnam)(202403AP140032)

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摘要

色烯并吡咯类化合物具有广泛的生理和药理活性. 发展了一种CuI催化下, 以1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)为促进剂, 室温下3-硝基色烯和环状β-烯胺酮通过[3＋2]环合反应合成分子多样性2H-色烯并吡咯化合物的新方法. 该反应具有良好官能团相容性、广泛底物普适性和温和反应条件等优点.

关键词： 铜催化; [3＋2]环合; 2H-色烯并吡咯; 3-硝基色烯; 烯胺酮

本文引用格式

梁婉婷 , 陈思怡 , 徐恩琪 , 陈雪冰 . 铜催化3-硝基色烯与烯胺酮环化反应合成2H-色烯并吡咯衍生物[J]. 有机化学, 2026 , 46(2) : 496 -506 . DOI: 10.6023/cjoc202507037

Abstract

Chromeno-pyrrole derivatives exhibit a wide range of biological and pharmacological activities. Herein, a novel approach to the synthesis of molecular diversity 2H-chromeno-pyrrole has been developed from [3＋2] cyclization of 3-nitrochromenes. The reaction is catalyzed by CuI with 2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine (DBN) as the promoter at room temperature. This reaction has the advantages of good functional group compatibility, broad substrate universality, and mild reaction conditions.

Key words： copper catalysis; [3＋2] cyclization; 2H-chromeno-pyrroles; 3-nitrochromenes; enaminones

吡咯及其衍生物是一类重要的含氮杂环化合物, 其骨架广泛存在于天然产物和药物分子中[1]. 且在农药[2]、染料、材料[3]等领域也有广泛的应用. 迄今为止, 许多合成吡咯及其衍生物的方法陆续被报道, 包括经典的Knorr 反应[4]、Paal-Knorr反应[5]、Hantzsch反应[6]和Barton-Zard反应[7], 以及最新的可见光催化、微波促进[8]、超声促进、过渡金属催化[9]、生物催化、区域控制合成[10]、电化学催化[11]等方法[12]. 但这些方法或多或少存在底物范围窄、目标化合物骨架单一等缺点. 因此, 继续发展高效合成分子多样性吡咯化合物的策略依然很有必要.
图1 具有药理活性的色烯并吡咯化合物

Figure 1 Chromene fused pyrrole compounds with pharmacological activity

色烯是一类含有苯并吡喃结构单元的含氧杂环化合物, 其结构单元广泛存在于天然产物中, 是很多药物分子的核心骨架[13]. 尤其是2H-色烯, 表现出抗病毒[14]、抗菌[15]、抗利什曼原虫[16]、抗肿瘤[17]、抗人类免疫缺陷病毒(HIV)[18]等生物活性, 且可作为酶抑制剂防止虫害[19]、用于治疗阿尔兹海默症[20]和帕金森病等抗神经退行性疾病. 现有研究表明, 色烯单元稠合杂环化合物展现出优于母体杂环化合物的生物活性[21]. 如含有色烯并吡啶结构的氨来沙诺(Amlexanox)[22]是常用抗过敏和局部抗溃疡剂; 含有色烯并呋喃结构的新丹参内酯(Neo-tanshinlactone)和补骨脂素(Psoralidin)[23]都是抗肿瘤药物的主要成分; 海洋生物碱Ningalin B和Lamellarin D均含有色烯并吡咯结构, 展现出多种生物活性, 包括细胞毒性、HIV-1整合酶抑制作用、多药耐药(MDR)逆转活性以及免疫调节功能(Figure 1)[24]. 鉴于吡咯类化合物、色烯类化合物以及色烯稠合杂环化合物均具有优异的生物活性, 依据活性叠加原理, 进一步探究将吡咯和色烯结构杂合在同一个分子中, 对于开发药物分子具有重要意义.
基于色烯并吡咯衍生物的重要生物活性, 发展上述化合物的合成方法受到人们的广泛关注. 在这些方法中, 3-硝基-2H-色烯因结构中含有硝基烯烃单元, 可依次经历迈克尔加成、硝基离去及 [3＋2]环化反应, 实现色烯并吡咯化合物的高效合成. 例如, 2018年Yan课题组[25]报道了一种吲哚乙胺、丙炔酸酯和3-硝基-2H-色烯在三氟甲磺酸催化下, 通过“一锅”三步反应合成2H-色烯并吡咯稠杂环化合物的方法(Scheme 1a). 同年, 该课题组[26]还发展了苯并噻嗪烯胺酯和3-硝基-2H-色烯在醋酸催化环化下, 合成官能化2H-色烯并吡咯化合物的方法(Scheme 1a). Kumar课题组[27]报道了一种以3-硝基-2H-色烯、苯胺和乙酰丙酮为原料, 使用FeCl3作为催化剂, 微波辐射合成2H-色烯并吡咯的方法(Scheme 1b). 另外一种常用的策略, 是从4-氯-3-硝基-2H-色烯酮出发, 经串联亲核取代/分子内环化反应, 合成色烯并吡咯化合物的方法(Scheme 1c). Yang课题组报道了以4-氯-3-硝基-2H-色烯酮为原料, 分别以苯乙醛[28a]、溴代苯乙酮[28b]、1-甲基异喹啉[28c]为底物, 通过催化偶联/硝基还原分子内环化合成2H-色烯酮并吡咯化合物的方法. 2010年, Langer等[29]报道了4-氯-3-硝基-2H-色烯酮与乙酰丙酮通过环加成反应合成2H-色烯酮并吡咯的方法. Xu课题组[30]则报道了4-氯-3-硝基-2H-色烯酮和炔在钯催化下, 通过连续偶联/环化反应合成2H-色烯酮并吡咯的方法. 尽管上述方法可以有效地合成色烯(酮)并吡咯化合物, 但大多数策略仍然存在反应条件苛刻、反应步骤多、底物普适性差的缺点, 因此, 发展简便、高效的构建结构新颖和分子多样性的2H-色烯并吡咯化合物的方法依然迫切需要.
图式1 色烯并吡咯的合成方法

Scheme 1 Synthetic method of chromeno fused pyrroles

烯胺酮作为一类简单易得的合成子, 因其含有独特的氮杂烯结构, 被广泛用于合成吡咯、吲哚、喹啉酮、吖啶、萘啶、噻唑、吡啶等多种杂环或者稠杂环[31]. 我们课题组[32]前期一直致力于发展基于烯胺酮的高效、绿色构建杂环化合物的方法. 本文发展了一种β-烯胺酮和3-硝基色烯(酮)在CuⅠ和DBN作用下, 温和条件下, 通过[3＋2]环合反应合成了一类分子多样性的色烯并吡咯化合物. 值得一提的是, 3-硝基色烯酮首次被用于通过上述反应方式合成目标化合物(Scheme 1d).

1 结果与讨论

1.1 反应条件优化

为了得到最优反应条件, 以苯环上4-位氯取代的烯胺酮(1a)和3-硝基-2-苯基-2H-色烯(2a)为基准底物, 对反应条件进行了筛选, 实验结果如表1所示.
表1 反应条件的优化a

Table 1 Optimization of reaction conditions

Entry Solvent Promoter Metal T/℃ Yieldb/%
1 EtOH — — r.t.~reflux N.R.
2 EtOH DBU CuCl2 r.t. 25
3 EtOH DBU CuBr r.t. 30
4 EtOH DBU CuI r.t. 30
5 EtOH DBU AgNO3 r.t. 28
6 EtOH DBU Fe2O3 r.t. 10
7 EtOH DBU FeCl3 r.t. 7
8 EtOH DBU InCl3 r.t. 26
9 CH3OH DBU CuI r.t. 25
10 Toluene DBU CuI r.t. 45
11 DMSO DBU CuI r.t. 40
12 CH3CN DBU CuI r.t. 45
13 DMF DBU CuI r.t. 15
14 1,4-Dioxane DBU CuI r.t. N.R.
15 THF DBU CuI r.t. 40
16 CH3CN DBN CuI r.t 51
17 CH3CN Cs2CO3 CuI r.t 38
18 CH3CN K2CO3 CuI r.t 35
19 CH3CN Piperidine CuI r.t 10
20 CH3CN TEA CuI r.t 20
21 CH3CN DABCO CuI r.t 10
22 CH3CN CF3COOH CuI r.t N.R.
23 CH3CN TsOH CuI r.t N.R.
24c CH3CN DBN CuI r.t. 44
25d CH3CN DBN CuI r.t. 50
26 CH3CN DBN CuI 60 45
27 CH3CN — CuI r.t N.R.
28 CH3CN DBN — r.t 5

a The reaction was performed with 1a (0.3 mmol), 2a (0.3 mmol), promoter (0.06 mmol), metal (0.03 mmol) and solvent (4 mL) for 4 h. b Isolated yield. N.R.=no reaction; c The amount of CuI added is 5 mol%. d The amount of CuI added is 20 mol%.

首先, 反应以无水乙醇作为溶剂, 在无金属无促进剂条件下进行, 结果表明, 无论在室温还是回流条件下, 反应都不能发生(Table 1, Entry 1). 然后, 继续以乙醇为溶剂, 以1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)为碱促进剂, 在不同铜金属催化剂(CuCl2, CuBr, CuI)作用下, 以25%~30%的产率得到了色烯并吡咯化合物3a (Table 1, Entries 2~4). 在此基础上, 进一步尝试了其他金属催化剂, 如AgNO3, Fe2O3, FeCl3, InCl3, 但反应效果均不如CuI (Table 1, Entries 5~8). 为了得到更合适的反应溶剂, 筛选了一系列反应溶剂, 如甲醇、甲苯、二甲基亚砜(DMSO)、乙腈、和N,N-二甲基甲酰胺(DMF)等, 实验结果表明, 多数溶剂均可以兼容该反应, 其中乙腈反应效果最好, 当使用1,4-二氧六环时没有监测到目标产物(Table 1, Entries 9~15). 随后, 考察了酸碱促进剂对反应的影响. 尝试有机碱DBN、哌啶、三乙胺、1,4-二氮杂二环[2.2.2]辛烷(DABCO), 无机碱Cs2CO3、K2CO3, 发现上述碱均能促进该反应发生, 且DBN更适用于该反应体系, 产率可达到51% (Table 1, Entries 16~21). 然而, 酸性催化剂, 如三氟乙酸和对甲基苯磺酸不能作用于上述反应(Table 1, Entries 22~23). 为进一步提高反应的产率, 研究了CuI的用量对目标产物产率的影响. 发现降低CuI的用量为0.05 equiv.时, 反应产率明显下降, 而增加CuI的用量为0.2 equiv.时, 反应产率无明显变化(Table 1, Entries 24~25). 尝试改变反应温度来提高反应产率, 结果表明, 升高温度反应产率有所下降, 室温是该反应体系最佳温度(Table 1, Entries 26). 最后, 考察了该反应在无促进剂或无金属催化的情况. 实验结果表明, 无促进剂DBN情况下, 该反应不能发生; 而在DBN作用下, 无CuI条件下, 该反应产率也仅为5% (Table 1, Entries 27~28). 最终确定最佳反应条件为乙腈作溶剂, 0.2 equiv. DBN为促进剂, 0.1 equiv. CuI为催化剂, 反应温度室温.

1.2. 反应底物扩充

在获得最优反应条件后, 对底物普适性进行探究. 首先, 考察了一系列不同取代基和取代位置的环状β-烯胺酮1. 结果表明, 这类底物均能以良好至适中的产率得到目标产物色烯并吡咯化合物3a~3p (表2). 此外, 通过X射线单晶衍射确认了3e的结构(CCDC:2354504). 如表2所示, 烯胺酮1的4-碳上不管是氢还是甲基取代, 目标产物都可以得到; 同样地, 烯胺酮1的N-芳环上不管有供电子基(OCH3, CH3)或者吸电子基(硝基、卤素), 均可以得到相应的目标化合物3. 从反应结果看, 烯胺酮取代基的电子效应和空间效应对该反应无明显影响. 接着, 考察了不同取代基的3-硝基-2-芳基-2H-色烯2. 实验结果表明, 当色烯2-位苯环上接有吸电子基(CF3, Cl)或者供电子甲氧基, 该反应都可以以中等产率顺利进行. 且当接有强吸电子的三氟甲基时, 反应产率略优于其他底物(3f~3h). 除此之外, 3-硝基-2-芳基-2H-色烯2的7-位上接有取代基时, 该反应也能够顺利进行(3i~3m). 此外, 链状烯胺酮也被用于该反应, 以40%的产率得到了化合物3q. 为进一步验证该反应的适用性, 以烯胺酮1a为底物开展了克级规模反应实验, 最终以 45%的产率得到目标化合物3a.
表2 烯胺酮和3-硝基色烯的底物适应性研究a,b

Table 2 Substrate scope of enaminones and 3-nitro-chromene

aReaction conditions: 1 (0.3 mmol), 2 (0.3 mmol), CuI (10.0 mol%), DBN (20.0 mol%) in CH3CN (3.0 mL) at r.t. for 1~3 h. b Isolated yields were based on 1. c 5 mmol scale.

为了进一步探究该反应的普适性, 3-硝基2-色烯酮4被用于上述反应. 如表3所示, 以中等至良好产率合成了10个吡咯并色烯酮化合物5a~5j. 研究中发现, 3-硝基2-色烯酮4与β-烯胺酮反应的时间比3-硝基2-色烯2的反应时间缩短一倍, 且产率均普遍提高. 推测3‑硝基‑2‑色烯酮4中羰基的吸电子共轭效应, 增强了色烯迈克尔加成受体中α‑碳原子的亲电性, 从而提高了反应效率. 值得一提的是, N-环丙基烯胺酮和环戊基烯胺酮均适用于该反应(5e, 5i, 5j).
表3 烯胺酮和3-硝基色烯酮反应结果a,b

Table 3 Reaction results of enaminone and 3-nitro-chromone

a Reaction conditions: 1 (0.3 mmol), 4 (0.3 mmol), CuI (10.0 mol%), DBN (20.0 mol%) in CH3CN (3.0 mL) at r.t. for 0.5~1 h. b Isolated yields were based on 1.

1.3 可能的反应机理

为了进一步了解该反应的可能机理, 以目标化合物5j的合成为例, 开展了相关的控制实验. 如Scheme 2所示, 往模型反应中添加过量的自由基捕获剂2,2,6,6-四甲基哌啶氧化物(TEMPO)或2,6-二叔丁基对甲酚(BHT), 该反应仍分别以62%和65%的产率顺利进行. 该结果表明反应可能不涉及自由基机理.
图式2 控制实验

Scheme 2 Controlled experiment

基于对文献调研[33]以及控制实验的结果, 以化合物5的合成为例, 提出了以下反应机理(Scheme 3): 首先是DBN夺取烯胺酮1氨基氮上的氢, 并通过烯胺-亚胺互变、酮-烯醇互变得到中间体A. 中间体A氧负离子与Cu＋结合得到中间体B, 进而与3-硝基色烯酮4发生迈克尔加成生成中间体C. 中间体C通过分子内环合得到中间体D, 而后经过脱水、消除HNO后得到目标产物吡咯并色烯酮化合物5.
图式3 合成化合物5的反应机理

Scheme 3 Plausible mechanism for the synthesis of compounds 5

2 结论

本文探索和发展了一种从简单易得合成子β-烯胺酮和3-硝基色烯(酮)出发, 以DBN为促进剂, 在CuI催化下通过[3＋2]环合反应合成2H-色烯并吡咯衍生物的方法. 上述方法具有反应条件温和, 底物范围广, 路线简洁等优点. 所合成化合物分子中兼具吡咯和色烯两种杂环骨架, 在医药领域中具有较好的潜在应用价值.

3 实验部分

3.1 仪器与试剂

反应使用电磁搅拌, 在烘干的玻璃仪器中进行; 使用XT4A型显微熔点测定仪(控温型)测定熔点; 使用Agilent CL/Msd TOF质谱仪测定MS; 使用Bruck DRX 400M, 500M或600M型核磁共振仪测定NMR, TMS作为内标, 氘代氯仿(CDCl3)作为溶剂. 实验所涉及试剂均为化学纯或分析纯, 溶剂用无水硫酸钠或分子筛干燥处理; 柱层析使用硅胶为青岛海洋化工(200~300目), 如果不做特别说明, 流动相均采用分析纯石油醚和乙酸乙酯; 反应监控用薄层色谱(TLC)方法, 青岛海洋化工厂生产的薄层层析板(GF254高效板).

3.2 实验方法

2H-色烯并吡咯稠杂环化合物的合成通法: 称取0.3 mmol烯胺酮1, 0.3 mmol 3-硝基色烯2或者4, 0.03 mmol CuI, 0.06 mmol DBN于15 mL圆底烧瓶中, 加入3 mL乙腈, 室温搅拌反应约0.5~3.0 h. TLC监测3-硝基色烯反应完全, 停止反应, 用乙酸乙酯(20 mL×3)萃取, 合并有机相, 无水硫酸钠干燥, 真空浓缩. 粗产品经柱层析[V(石油醚)∶V(乙酸乙酯)=10∶1]得纯净固体, 产率34%~71%. 所有化合物的结构都经过核磁共振、熔点以及高分辨质谱表征.
7-(4-氯苯基)-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3a): 白色固体, 69.5 mg, 51% yield. m.p. 200~202 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.77~8.74 (m, 1H, ArH), 7.48~7.19 (m, 2H, ArH), 7.17~7.08 (m, 4H, ArH), 6.97 (t, J=3.6 Hz, 2H, ArH), 6.92 (d, J=7.2 Hz, 2H, ArH), 6.69~6.67 (m, 1H, ArH), 6.52~6.25 (m, 1H, ArH), 5.95 (s, 1H, CH), 2.45 (d, J=16.4 Hz, 1H, CH2), 2.40 (d, J=15.6 Hz, 1H, CH2), 2.35 (d, J=15.4 Hz, 1H, CH2), 2.30 (d, J=16.4 Hz, 1H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.4, 149.3, 137.7, 134.2, 133.1, 128.7, 127.8, 127.6, 127.2, 126.6, 126.5, 126.4, 121.0, 119.0, 115.5, 115.1, 113.0, 73.5, 52.2, 36.7, 34.0, 27.7, 27.0; HRMS (ESI-TOF) calcd for C29H23ClFNO2Na [M＋Na]＋ 476.1388, found 476.1392.
7-(3-氯苯基)-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3b): 白色固体, 58.6 mg, 43% yield. m.p. 180~183; 1H NMR (400 MHz, CDCl3) δ: 8.79~8.73 (m, 1H, ArH), 7.30 (d, J=8.0, 1H, ArH), 7.15~7.08 (m, 3H, ArH), 6.98~6.95 (m, 2H, ArH), 6.93~6.88 (m, 2H, ArH), 6.71~6.67 (m, 1H, ArH), 6.65~6.57 (m, 1H, ArH), 5.97 (s, 1H, CH), 2.44 (d, J=16.0 Hz, 1H, CH2), 2.42 (d, J=16.0 Hz, 1H, CH2), 2.36 (d, J=16.4 Hz, 1H, CH2), 2.31 (d, J=16.4 Hz, 1H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.3, 149.5, 144.1, 137.8, 135.7, 134.1, 129.4, 128.4, 127.6, 127.2, 126.5, 126.5,126.4, 124.7, 121.0, 115.5, 115.1, 113.1, 73.6, 52.3, 35.7, 34.0, 27.7, 27.0; HRMS (ESI-TOF) calcd for C29H24ClNO2Na [M＋Na]＋ 476.1388, found 476.1394.
7-(4-溴苯基)-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3c): 白色固体, 71.8 mg, 48% yield. m.p. 220~223 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.77~8.74 (m, 1H, ArH), 7.62~7.17 (m, 2H, ArH), 7.15~7.06 (m, 4H, ArH), 6.94 (t, J=4.0 Hz, 2H, ArH), 6.91 (d, J=3.8 Hz, 2H, ArH), 6.69~6.65 (m, 1H, ArH), 6.47~6.13 (m, 1H, ArH), 5.94 (s, 1H, CH), 2.41 (d, J=16.0 Hz, 1H, CH2), 2.36 (d, J=16.0 Hz, 1H, CH2), 2.32 (d, J=17.6 Hz, 1H, CH2), 2.27 (d, J=16.4 Hz, 1H, CH2), 1.01 (s, 3H, CH3), 0.98 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.3, 149.4, 144.2, 137.7, 133.6, 131.7, 128.0, 127.8, 127.6, 127.1, 126.6, 126.5, 126.4, 122.2, 121.0, 119.1, 115.5, 115.1, 113.0, 76.3, 75.7, 73.5, 52.2, 35.6, 34.0, 27.7, 27.1; HRMS (ESI-TOF) calcd for C29H24Br- NO2Na [M＋Na]＋ 520.0883, found 520.0887.
7-(3-氟苯基)-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3d): 白色固体, 51.6 mg, 42% yield. m.p. 218~220 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.80~8.75 (m, 1H, ArH), 7.19 (s, 1H, ArH), 7.16~7.07 (m, 3H, ArH), 7.07~7.01 (m, 1H, ArH), 6.98~6.95 (m, 2H, ArH), 6.93 (d, J=6.8 Hz, 2H, ArH), 6.70~6.67 (m, 1H, ArH), 5.99 (s, 1H, CH), 2.57~2.53 (m, 2H, CH2), 2.51 (t, J=6.0 Hz, 2H, CH2), 2.13~2.01 (m, 2H, CH2); 13C NMR (101 MHz, CDCl3) δ: 192.9, 161.5 (d, 1JC-F=249.0 Hz), 160.3, 149.4, 145.1, 137.7, 136.0, 129.7, 126.6, 127.8, 127.5, 127.0, 126.7, 126.5,122.3, 121.0, 119.0, 116.2, 115.5, 115.4 (d, 2JC-F=21.0 Hz), 115.2 (d, 2JC-F=21.0 Hz), 113.3, 76.3, 75.7, 73.5, 38.2, 22.3, 21.9; HRMS (ESI-TOF) calcd for C27H20FNO2Na [M＋Na]＋ 432.1370, found 432.1374.
7-(4-氯苯基)-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3e): 白色固体, 61.3 mg, 48% yield. m.p. 204~205 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.79~8.77 (m, 1H, ArH), 7.36~7.19 (m, 2H, ArH), 7.16~7.08 (m, 4H, ArH), 6.96 (t, J=6.4 Hz, 2H, ArH), 6.93 (d, J=6.8 Hz, 2H, ArH), 6.69~6.66 (m, 1H, ArH), 6.54~6.25 (m, 1H, ArH), 5.94 (s, 1H, CH), 2.65~2.55 (m, 2H, CH2), 2.54~2.44 (m, 2H, CH2), 2.14~1.96 (m, 2H, CH2); 13C NMR (101 MHz, CDCl3) δ: 192.9, 149.4, 145.3, 137.7, 137.2, 133.1, 128.7, 127.8, 127.7, 127.6, 127.1, 126.6, 126.5, 126.4, 121.0, 119.1, 116.2, 115.5, 113.2, 73.4, 38.2, 22.3, 21.8; HRMS (ESI-TOF) calcd for C27H20ClNO2Na [M＋Na]＋ 448.1075, found 448.1082.
7-苯基-6-(2-(三氟甲基)苯基)-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3f): 白色固体, 71.7 mg, 52% yield. m.p. 241~243 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.82~8.77 (m, 1H, ArH), 7.52~7.46 (m, 1H, ArH), 7.38~7.24 (m, 5H, ArH), 7.17~7.05 (m, 2H, ArH), 6.98~6.91 (m, 2H, ArH), 6.65~6.57 (m, 1H, ArH), 6.41 (s, 1H, CH), 6.39~6.36 (m, 1H, ArH), 2.62~2.54 (m, 2H, CH2), 2.51~2.46 (m, 2H, CH2), 2.13~2.01 (m, 2H, CH2); 13C NMR (101 MHz, CDCl3) δ: 193.0, 148.7, 145.7, 134.9, 134.1, 131.0, 129.3, 128.4, 127.8, 127.0, 126.7, 126.4, 126.3, 126.1, 125.1, 121.2, 119.2, 115.2 (q, 1JC-F=60.0 Hz), 114.1, 68.0, 38.2, 22.3, 21.8; HRMS (ESI-TOF) calcd for C28H20F3NO2Na [M＋Na]＋ 482.1338, found 482.1347.
7-(2-氟苯基)-9,9-二甲基-6-(2-(三氟甲基)苯基- 7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3g): 白色固体, 92.5 mg, 61% yield. m.p. 227~228 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.85~8.73 (m, 1H, ArH), 7.55~7.45 (m, 1H, ArH), 7.34~7.23 (m, 3H, ArH), 7.16~7.05 (m, 2H, ArH), 7.00~6.91 (m, 2H, ArH), 6.78~6.67 (m, 1H, ArH), 6.66~6.59 (m, 1H, ArH), 6.40 (s, 1H, CH), 6.34~6.27 (m, 1H, ArH), 2.45 (d, J=16.0 Hz, 1H, CH2), 2.40 (d, J=16.4 Hz, 1H, CH2), 2.30 (s, 2H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.3, 161.6 (d, 1JC-F=249.0 Hz), 160.4, 148.7, 144.8, 134.9, 131.2, 130.1 (d, 3JC-F=3.0 Hz), 129.4, 128.3, 128.2, 127.9, 127.0, 126.8, 126.6, 126.4, 125.4, 115.3 (q, 1JC-F=60.0 Hz), 121.2, 118.9, 115.9, 115.9, 114.8, 114.0, 68.1, 52.2, 35.6, 34.0, 27.8, 27.1; HRMS (ESI-TOF) calcd for C30H23F4NO2Na [M＋Na]＋ 528.1557, found 528.1564.
7-(4-氯苯基)-9,9-二甲基-6-(3-(三氟甲基)苯基)- 7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3h): 白色固体, 101.8 mg, 65% yield. m.p. 255~257 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.80~8.74 (m, 1H, ArH), 7.45~7.49 (m, 1H, ArH), 7.33~7.24 (m, 3H, ArH), 7.15~7.08 (m, 2H, ArH), 6.99~6.92 (m, 2H, ArH), 6.66~6.60 (m, 1H, ArH), 6.41 (s, 1H, CH), 6.22~6.17 (m, 1H, ArH), 2.46 (d, J=16.0 Hz, 1H, CH2), 2.41 (d, J=16.0 Hz, 1H, CH2), 2.32 (s, 2H, CH2), 1.05 (s, 3H, CH3), 1.02 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.3, 148.7, 144.5, 134.9, 134.5, 132.7, 131.2, 129.2, 128.4, 127.9, 127.7, 126.9, 126.7, 126.4, 126.2, 125.4 (q, 1JC-F=50.0 Hz), 121.2, 118.9, 115.9, 115.0, 114.2, 68.0, 52.4, 35.6, 34.0, 27.6, 27.1; HRMS (ESI-TOF) calcd for C30H24Cl- F3NO2 [M＋H]＋ 544.1262, found 544.1266.
7-(2-氯苯基)-3-氟-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3i): 白色固体, 73.6 mg, 52% yield. m.p. 204~207 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.78 (dd, J=8.8, 6.8 Hz, 1H, ArH), 7.46 (d, J=8.0 Hz, 1H, ArH), 7.25 (t, J=8.0 Hz, 1H, ArH), 7.13 (t, J=8.0 Hz, 1H, ArH), 7.06 (t, J=8.0 Hz, 2H, ArH), 6.92~6.88 (m, 3H, ArH), 6.66~6.62 (m, 1H, ArH), 6.48~6.40 (m, 2H, ArH), 5.89 (s, 1H, CH), 2.44 (d, J=16.4 Hz, 1H, CH2), 2.37 (d, J=16.4 Hz, 1H, CH2), 2.29 (d, J=16.4 Hz, 1H, CH2), 2.11 (d, J=16.4 Hz, 1H, CH2), 1.02 (s, 3H, CH3), 1.00 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.4, 161.0 (d, 1JC-F=243.0 Hz), 150.91 (d, 3JC-F=13.0 Hz), 144.7. 137.8, 132.3, 131.6, 129.2, 129.2, 127.9, 127.5, 127.4. 127.3, 126.6, 126.5, 126.3, 115.3, 114.8, 112.4. 107.3 (d, 2JC-F=20.0 Hz), 103.0 (d, 2JC-F=25.0 Hz), 74.4, 52.2, 35.2, 34.0, 28.2, 26.4; HRMS (ESI-TOF) calcd for C29H23ClFNO2Na [M＋Na]＋ 494.1294, found 494.1293.
3-氟-7-(2-氟苯基)-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3j): 白色固体, 79.3 mg, 58% yield. m.p. 241~243 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.77 (dd, J=8.4, 6.8 Hz, 1H, ArH), 7.19 (s, 1H, ArH), 7.17~7.08 (m, 4H, ArH), 6.89 (d, J=6.8 Hz, 2H, ArH), 6.78~6.68 (m, 1H, ArH), 6.67~6.61 (m, 1H, ArH), 6.41 (dd, J=10.0, 2.8 Hz, 2H, ArH), 5.95 (s, 1H, CH), 2.44 (d, J=16.0 Hz, 1H, CH2), 2.38 (d, J=16.0 Hz, 1H, CH2), 2.34 (d, J=16.8 Hz, 1H, CH2), 2.28 (d, J=16.4 Hz, 1H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 192.4, 161.5 (d, 1JC-F=249.0 Hz), 161.0 (d, 1JC-F=243.0 Hz), 150.7, 150.5, 144.4, 137.5, 130.5, 130.4, 128.0, 127.7, 127.5, 127.4, 126.5, 126.4, 115.5 (d, 2JC-F=23.0 Hz), 114.7, 112.4, 107.4 (d, 2JC-F=21.0 Hz), 103.3 (d, 2JC-F=25.0 Hz), 73.8, 52.2, 35.6, 34.0, 27.7, 27.0; HRMS (ESI-TOF) calcd for C29H23- F2NO2Na [M＋Na]＋ 478.1589, found 478.1594.
3-氟-9,9-二甲基-7-(4-硝基苯基)-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3k): 白色固体, 69.5 mg, 48% yield. m.p. 248~250 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.76 (dd, J=8.8, 7.2 Hz, 1H, ArH), 8.17~8.11 (m, 2H, ArH), 7.14 (s, 2H, ArH), 7.46~7.17 (m, 3H, ArH), 7.15~7.09 (m, 2H, ArH), 6.94~6.91 (m, 2H, ArH), 6.71~6.62 (m, 1H, ArH), 6.46~6.38 (m, 1H, ArH), 5.98 (s, 1H, CH), 2.46 (d, J=16.0 Hz, 1H, CH2), 2.38 (d, J=16.0 Hz, 1H, CH2), 2.34 (d, J=16.8 Hz, 1H, CH2), 2.28 (d, J=16.4 Hz, 1H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 193.4, 162.2 (d, 1JC-F=244.0 Hz), 151.7 (d, 3JC-F=9.0 Hz), 144.7, 144.8, 141.1, 138.0, 128.9, 128.4, 127.6, 127.0, 124.9, 116.6, 116.0, 114.6, 108.7 (d, 2JC-F=21.0 Hz), 104.5 (d, 2JC-F=25.0 Hz), 74.7, 53.1, 36.9, 35.2, 28.6, 28.1; HRMS (ESI- TOF) calcd for C29H23FN2O4Na [M＋Na]＋ 505.1534, found 505.1539.
3-氟-7-(4-甲氧基苯基)-9,9-二甲基-6-苯基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3l): 白色固体, 49.1 mg, 35% yield. m.p. 204~207 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.76 (dd, J=8.8, 7.2 Hz, 1H, ArH), 7.19~7.09 (m, 4H, ArH), 6.90 (d, J=6.8 Hz, 3H, ArH), 6.67~6.62 (m, 2H, ArH), 6.42 (dd, J=12.0, 8.0 Hz, 1H, ArH), 5.96 (s, 1H, CH), 3.57 (s, 3H, OCH3), 2.44 (d, J=16.0 Hz, 1H, CH2), 2.36 (d, J=16.4 Hz, 1H, CH2), 2.32 (d, J=16.8 Hz, 1H, CH2), 2.28 (d, J=16.8 Hz, 1H, CH2), 1.04 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 193.5, 162.0 (d, 1JC-F=243.0 Hz), 160.0, 151.6, 145.7, 138.8, 128.8, 128.5, 128.4, 128.1, 127.7, 127.5, 116.6, 115.4, 114.6, 113.0, 108.4 (d, 2JC-F=21.0 Hz), 104.3 (d, 2JC-F=25.0 Hz), 74.8, 55.5, 53.3, 36.7, 35.1, 28.7, 28.0; HRMS (ESI-TOF) calcd for C30H26FNO3Na [M＋Na]＋ 490.1789, found 490.1795.
3-氟-7-(4-氟苯基)-6-苯基-7,8,9,10-四氢色烯并[3,4- b]吲哚-11(6H)-酮(3m): 白色固体, 66.7 mg, 52% yield. m.p. 217~220 ℃; 1H NMR (400 MHz, CDCl3) δ: 9.11 (dd, J=12.0, 8.0 Hz, 1H, ArH), 7.19 (s, 1H, ArH), 7.18~7.08 (m, 4H, ArH), 6.79~6.70 (m, 3H, ArH), 6.50~6.60 (m, 1H, ArH), 6.42 (dd, J=8.0, 4.0 Hz, 1H, ArH), 5.94 (s, 1H, CH), 2.52~2.41 (m, 4H, CH2), 1.89~1.84 (m, 2H, CH2); 13C NMR (101 MHz, CDCl3) δ: 192.9, 161.6 (d, 1JC-F=249.0 Hz), 161.1 (d, 1JC-F=243.0 Hz), 150.7, 150.6, 145.4, 137.5, 130.5, 128.0, 127.6, 127.5, 127.4, 126.5, 126.3, 115.7 (d, 2JC-F=22.0 Hz), 115.6 (d, 2JC-F=23.0 Hz), 112.6, 107.5 (d, 2JC-F=21.0 Hz), 103.3 (d, 2JC-F=25.0 Hz), 73.8, 38.2, 22.3, 21.8; HRMS (ESI-TOF) calcd for C27H19F2NO2Na [M＋Na]＋ 450.1276, found 450.1285.
6-(2-氯苯基)-7-(3-氟苯基)-9,9-二甲基-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3n): 白色固体, 70.6 mg, 53% yield. m.p. 214~216 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.79~8.77 (m, 1H, ArH), 7.29~7.15 (m, 2H, ArH), 7.10~7.02 (m, 2H, ArH), 7.00~6.99 (m, 2H, ArH), 6.97~6.94 (m, 2H, ArH), 6.69~6.65 (m, 1H, ArH), 6.53 (s, 1H, CH), 2.55 (d, J=5.2 Hz, 1H, CH2), 2.54 (d, J=5.6 Hz, 1H, CH2), 2.51 (d, J=6.0 Hz, 1H, CH2), 2.48 (d, J=5.6 Hz, 1H, CH2), 2.09~2.04 (m, 2H, CH2); 13C NMR (101 MHz, CDCl3) δ: 192.8, 161.5 (d, 1JC-F=249.0 Hz), 149.2, 145.3, 135.7, 135.6, 134.4, 132.1, 129.9, 129.8, 129.2, 129.0, 128.4, 126.8, 126.4, 126.1, 122.0, 121.2, 119.0, 116.2, 115.4 (d, 2JC-F=21.0 Hz), 113.8 (d, 2JC-F=24.0 Hz), 69.2, 38.2, 22.3, 21.8; HRMS (ESI-TOF) calcd for C27H19ClFNO2Na [M＋Na]＋ 466.0981., found 466.0987.
7-(4-氯苯基)-9,9-二甲基-6-(3,4,5-三甲氧基苯基)- 7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3o): 白色固体, 55.5 mg, 34% yield. m.p. 229~230 ℃; 1H NMR (500 MHz, CDCl3) δ: 8.86~8.78 (m, 1H, ArH), 7.64~7.18 (m, 3H, ArH), 7.11~6.94 (m, 2H, ArH), 6.85~6.71 (m, 1H, ArH), 6.70~6.30 (m, 1H, ArH), 6.21~6.10 (m, 2H, ArH), 5.96 (s, 1H, CH), 3.81~3.72 (m, 3H, CH3), 3.66~3.55 (m, 6H, CH3), 2.43~2.29 (m, 2H, CH2), 2.19~2.09 (m, 1H, CH2), 2.06~1.98 (m, 1H, CH2), 1.15~0.99 (m, 6H, CH3); 13C NMR (125 MHz, CDCl3) δ: 193.2, 153.2, 150.7, 145.4, 138.5, 125.3, 134.6, 134.4, 129.7, 128.9, 128.5, 127.7, 127.5, 122.1, 119.8, 116.4, 116.1, 114.0, 104.7, 75.1, 60.7, 56.0, 53.3, 36.7, 35.0, 28.5, 28.1; HRMS (ESI- TOF) calcd for C32H30ClNO5Na [M＋Na]＋ 566.1705, found 566.1713.
7-(4-氯苯基)-6-(3,4,5-三甲氧基苯基)-7,8,9,10-四氢色烯并[3,4-b]吲哚-11(6H)-酮(3p): 白色固体, 78.9 mg, 51% yield. m.p. 224~226 ℃; 1H NMR (500 MHz, CDCl3) δ: 8.81~8.73 (m, 1H, ArH), 7.48~7.06 (m, 3H, ArH), 7.05~6.92 (m, 2H, ArH), 6.80~6.69 (m, 1H, ArH), 6.63~6.28 (m, 1H, ArH), 6.11 (s, 2H, ArH), 5.88 (s, 1H, CH), 3.70 (s, 3H, CH3), 3.54 (s, 6H, CH3), 2.62~2.50 (m, 2H, CH2), 2.50~2.41 (m, 2H, CH2), 2.08~2.00 (m, 2H, CH2); 13C NMR (125 MHz, CDCl3) δ: 193.8, 153.2, 150.8, 148.4, 138.5, 135.2, 134.6, 34.4, 129.6, 128.9, 128.4, 127.7, 127.5, 122.1, 119.9, 117.2, 116.4, 114.0, 104.7, 75.1, 60.7, 56.0, 39.2, 23.3, 22.8; HRMS (ESI-TOF) calcd for C30H26ClNO5Na [M＋Na]＋ 538.1392, found 538.1400.
1-(4-苯基-3-(4-甲基苯基)-3,4-二氢色烯并[3,4-b]吡咯-1-基)苯基甲酮(3q): 白色固体, 53.0 mg, 40% yield. m.p. 173~175 ℃; 1H NMR (400 MHz, CDCl3) δ: 8.23 (d, J=8.0 Hz, 1H, ArH), 7.86 (d, J=8.0 Hz, 2H, ArH), 7.47 (t, J=8.0 Hz, 1H, ArH), 7.39 (t, J=8.0 Hz, 2H, ArH), 7.20~7.12 (m, 4H, ArH), 7.12~7.06 (m, 2H, ArH), 6.99~6.91 (m, 1H, ArH), 6.92~6.82 (m, 3H, ArH), 6.77~6.67 (m, 1H, ArH), 6.12 (s, 1H, CH), 2.26 (s, 3H, CH3); 13C NMR (101 MHz, CDCl3) δ: 190.4, 159.3, 128.5, 127.7, 127.5, 127.2, 128.8, 126.6, 125.5, 124.0, 120.9, 120.1, 119.8, 116.1, 115.4, 72.8, 20.0; HRMS (ESI-TOF) calcd for C31H24NO2 [M＋H]＋ 442.1802, found 442.1806.
7-(4-氟苯基)-9,9-二甲基-7,8,9,10-四氢色烯并[3,4- b]吲哚-6,11-二酮(5a): 白色固体, 55.2 mg, 49% yield. m.p. 237~240 ℃; 1H NMR (600 MHz, CDCl3) δ: 9.01 (d, J=8.4 Hz, 1H, ArH), 7.69 (d, J=8.4 Hz, 1H, ArH), 7.51 (t, J=7.8 Hz, 1H, ArH), 7.35 (t, J=7.8 Hz, 1H, ArH), 7.25~7.15 (m, 4H, ArH), 2.46 (s, 2H, CH2), 2.35 (s, 2H, CH2), 1.00 (s, 6H, CH3); 13C NMR (151 MHz, CDCl3) δ: 195.4, 163.7, 162.0, 157.7, 155.1, 142.9, 133.2, 130.1, 130.0, 129.6, 128.7, 126.4, 123.8, 123.1, 117.6, 117.4, 112.2, 111.6, 51.4, 43.6, 32.8, 28.1; HRMS (ESI-TOF) calcd for C23H18FNO3Na [M＋Na]＋ 398.1163, found 398.1171.
7-(2-氯苯基)-9,9-二甲基-7,8,9,10-四氢色烯并[3,4- b]吲哚-6,11-二酮(5b): 白色固体, 68.2 mg, 58% yield. m.p. 259~260 ℃; 1H NMR (600 MHz, CDCl3) δ: 9.05 (d, J=8.4 Hz, 1H, ArH), 7.62~7.58 (m, 2H, ArH), 7.52 (t, J=7.8 Hz, 1H, ArH), 7.48~7.44 (m, 2H, ArH), 7.37 (t, J=7.8 Hz, 1H, ArH), 7.30~7.25 (m, 1H, ArH), 2.49 (s, 2H, CH2), 2.38 (d, J=8.4, 17.4 Hz, 1H, CH2), 2.21 (d, J=17.4 Hz, 1H, CH2), 1.02 (s, 3H, CH3), 1.01 (s, 3H, CH3); 13C NMR (151 MHz, CDCl3) δ: 195.4, 157.7, 154.3, 151.1, 142.9, 135.1, 132.5, 131.2, 131.0, 129.9, 129.6, 128.7, 126.8, 123.8, 123.1, 112.3, 111.7, 51.5, 42.7, 32.7, 28.9, 27.4; HRMS (ESI-TOF) calcd for C23H18ClNO3Na [M＋Na]＋ 414.0867, found 414.0870.
7-(4-氯苯基)-9,9-二甲基-7,8,9,10-四氢色烯并[3,4- b]吲哚-6,11-二酮(5c): 白色固体, 56.4 mg, 48% yield. m.p. 246~248 ℃; 1H NMR (400 MHz, CDCl3) δ: 9.03 (d, J=8.4 Hz, 1H, ArH), 7.64~7.57 (m, 1H, ArH), 7.56~5.48 (m, 3H, ArH), 7.36 (t, J=8.0 Hz, 1H, ArH), 7.14 (d, J=8.8 Hz, 2H, ArH), 2.48 (s, 2H, CH2), 2.35 (s, 2H, CH2), 1.01 (s, 6H, CH3); 13C NMR (151 MHz, CDCl3) δ: 194.2, 158.7, 153.9, 149.7, 141.8, 134.8, 134.7, 129.6, 128.6, 128.5, 127.7, 125.6, 122.8, 122.0, 111.2, 110.6, 50.5, 42.6, 31.8, 27.1; HRMS (ESI-TOF) calcd for C23H18ClNO3Na [M＋Na]＋ 414.0867, found 414.0877.
7-(3-溴苯基)-9,9-二甲基-7,8,9,10-四氢色烯并[3,4- b]吲哚-6,11-二酮(5d): 白色固体, 53.7 mg, 41% yield. m.p. 265~270 ℃; 1H NMR (600 MHz, CDCl3) δ: 9.12 (d, J=8.4 Hz, 1H, ArH), 7.70 (dd, J=16.8, 7.8 Hz, 2H, ArH), 7.60 (t, J=7.8 Hz, 1H, ArH), 7.50 (t, J=7.8 Hz, 1H, ArH), 7.47~7.42 (m, 2H, ArH), 7.23 (d, J=7.2 Hz, 2H, ArH), 2.56 (s, 2H, CH2), 2.46 (d, J=17.4 Hz, 1H, CH2), 2.41 (d, J=17.4 Hz, 1H, CH2), 1.10 (s, 3H, CH3), 1.09 (s, 3H, CH3); 13C NMR (151 MHz, CDCl3) δ: 195.4, 157.7, 154.9, 150.7, 142.8, 138.5, 133.0, 131.5, 131.4, 129.6, 128.7, 123.8, 123.7, 123.0, 112.3, 111.7, 77.3, 76.9, 51.5, 43.5, 32.9, 28.3, 28.0; HRMS (ESI-TOF) calcd for C23H18BrNO3Na [M＋Na]＋ 458.0362, found 458.0364.
7-环丙基-9,9-二甲基-7,8,9,10-四氢色烯并[3,4-b]吲哚-6,11-二酮(5e): 白色固体, 38.6 mg, 40% yield. m.p. 219~221 ℃; 1H NMR (500 MHz, CDCl3) δ: 9.06~9.01 (m, 1H, ArH), 7.67~7.61 (m, 1H, ArH), 7.57~7.51 (m, 1H, ArH), 7.42~7.36 (m, 1H, ArH), 3.14~3.12 (m, 2H, CH2), 3.06~3.01 (m, 1H, CH), 2.58~2.55 (m, 2H, CH2), 1.46~1.41 (m, 2H, CH2), 1.20 (s, 3H, CH3), 1.19 (s, 3H, CH3), 1.01~0.96 (m, 2H, CH2); 13C NMR (125 MHz, CDCl3) δ: 195.2,157.5, 156.1, 153.4, 142.2, 129.1, 128.6, 125.5, 123.5, 123.2, 112.0, 111.6, 51.5, 42.4, 42.4, 33.0, 28.7, 28.2, 11.1; HRMS (ESI-TOF) calcd for C20H19N- O3Na [M＋Na]＋ 344.1257, found 344.1259.
7-(3-氟苯基)-7,8,9,10-四氢色烯并[3,4-b]吲哚-6,11-二酮(5f): 白色固体, 45.9 mg, 44% yield. m.p. 254~257 ℃; 1H NMR (600 MHz, CDCl3) δ: 9.08 (d, J=8.4 Hz, 1H, ArH), 7.69 (d, J=8.4 Hz, 1H, ArH), 7.62~7.56 (m, 2H, ArH), 7.44 (t, J=7.8 Hz, 1H, ArH), 7.30~7.26 (m, 1H, ArH), 7.12 (d, J=7.8 Hz, 1H, ArH), 7.07 (d, J=8.4 Hz, 1H, ArH), 2.69 (t, J=6.0 Hz, 2H, CH2), 2.64~2.55 (m, 2H, CH2), 2.18~2.07 (m, 2H, CH2); 13C NMR (151 MHz, CDCl3) δ: 195.2, 163.3 (d, 1JC-F=249.0 Hz), 162.5, 157.7, 154.6, 152.2, 142.9, 138.6, 138.5, 131.5, 131.5, 129.6, 128.7, 124.2, 124.2, 123.8, 123.1, 117.0 (d, 2JC-F=21.0 Hz), 116.1 (d, 2JC-F=22.5 Hz), 112.6, 112.3, 37.9, 30.0, 21.5; HRMS (ESI-TOF) calcd for C21H14FN- O3Na [M＋Na]＋ 370.0850, found 370.0857.
7-(4-氟苯基)-7,8,9,10-四氢色烯并[3,4-b]吲哚-6,11-二酮(5g): 白色固体, 40.6 mg, 39% yield. m.p. 238~242 ℃; 1H NMR (600 MHz, CDCl3) δ: 9.00 (d, J=6.0 Hz, 1H, ArH), 7.66~7.52 (m, 1H, ArH), 7.51~7.42 (m, 1H, ArH), 7.36~7.28 (m, 1H, ArH), 7.27~7.16 (m, 4H, ArH), 2.75~2.57 (m, 2H, CH2), 2.56~2.42 (m, 2H, CH2), 2.17~1.99 (m, 2H, CH2); 13C NMR (151 MHz, CDCl3) δ: 195.2, 163.9 (d, 1JC-F=249.0 Hz), 157.6, 154.9, 152.9, 143.0, 133.2, 130.1, 130.1, 129.5, 128.7, 126.8, 123.8, 123.1, 117.4 (d, 1JC-F=25.0 Hz), 117.3 (d, 1JC-F=25.0 Hz), 112.6, 112.2, 37.8, 30.2, 21.5; HRMS (ESI-TOF) calcd for C21H14FNO3Na [M＋Na]＋ 370.0850, found 370.0856.
7-(3-氯苯基)-7,8,9,10-四氢色烯并[3,4-b]吲哚-6,11-二酮(5h): 白色固体, 54.6 mg, 50% yield. m.p. 280~282 ℃; 1H NMR (600 MHz, CDCl3) δ: 8.99 (d, J=7.8 Hz, 1H, ArH), 7.60 (d, J=8.4 Hz, 1H, ArH), 7.52 (t, J=7.2 Hz, 1H, ArH), 7.50~7.45 (m, 2H, ArH), 7.36 (t, J=6.9 Hz, 1H, ArH), 7.26 (s, 1H, ArH), 7.19~7.12 (m, 1H, ArH), 2.67~2.58 (m, 2H, CH2), 2.56~2.44 (m, 2H, CH2), 2.10~2.00 (m, 2H, CH2); 13C NMR (151 MHz, CDCl3) δ: 194.1, 156.5, 153.5, 151.4, 141.8, 137.2, 134.7, 130.1, 128.5, 125.6, 122.7, 121.9, 111.5, 111.2, 36.7, 29.0, 20.3; HRMS (ESI-TOF) calcd for C21H14ClNO3Na [M＋Na]＋ 386.0554, found 386.0551.
7-(4-氯苯基)-8,9-二氢-6H-色烯并[3,4-b]环戊二烯[d]吡咯-6,10(7H)-二酮(5i): 白色固体, 65.0 mg, 62% yield. m.p. 254~256 ℃; 1H NMR (600 MHz, CDCl3) δ: 8.68 (d, J=7.8 Hz, 1H, ArH), 7.65~7.58 (m, 4H, ArH), 7.44 (t, J=7.8 Hz, 1H, ArH), 7.34 (d, J=8.4 Hz, 2H, ArH), 2.86~2.74 (m, 2H, CH2), 2.74~2.66 (m, 2H, CH2); 13C NMR (151 MHz, CDCl3) δ: 199.6, 163.9, 157.4, 154.7, 142.4, 139.1, 134.4, 130.5, 130.0, 129.2, 126.6, 124.8, 124.2, 122.4, 114.6, 112.4, 77.3, 76.9, 34.9, 27.1; HRMS (ESI-TOF) calcd for C20H12ClNO3Na [M＋Na]＋ 372.0398, found 372.0402.
7-(2-溴苯基)-8,9-二氢-6H-色烯并[3,4-b]环戊二烯[d]吡咯-6,10(7H)-二酮(5j): 白色固体, 84.0 mg, 71% yield. m.p. 271~273 ℃; 1H NMR (600 MHz, CDCl3) δ: 8.53 (d, J=7.8 Hz, 1H, ArH), 7.65 (d, J=8.4 Hz, 2H, ArH), 7.69~7.46 (m, 2H, ArH), 7.36~7.30 (m, 1H, ArH), 7.20 (d, J=9.0 Hz, 2H, ArH), 2.76~2.64 (m, 2H, CH2), 2.62~2.56 (m, 2H, CH2); 13C NMR (151 MHz, CDCl3) δ: 199.6, 163.9, 157.3, 154.6, 142.3, 135.0, 133.4, 130.0, 129.5, 126.6, 124.7, 124.2, 124.1, 122.3, 114.5, 112.3, 77.3, 76.7, 34.9, 27.1; HRMS (ESI-TOF) calcd for C20H12- BrNO3Na [M＋Na]＋ 415.9893, found 415.9898.
辅助材料(Supporting Information) 化合物3a~3q, 5a~5j的1H NMR, 13C NMR谱图. 这些材料可以免费从本刊网站(http://sioc-journal.cn/)上下载.
(Cheng, F.)

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