CN108440373B - 一种铁催化的氰烷基吲哚啉及其制备方法 - Google Patents

一种铁催化的氰烷基吲哚啉及其制备方法 Download PDF

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CN108440373B
CN108440373B CN201810243046.4A CN201810243046A CN108440373B CN 108440373 B CN108440373 B CN 108440373B CN 201810243046 A CN201810243046 A CN 201810243046A CN 108440373 B CN108440373 B CN 108440373B
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梁德强
王宝玲
李维莉
马银海
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Abstract

本发明属于化学材料技术领域，公开了一种铁催化的氰烷基吲哚啉及其制备方法，以非活化双键作为自由基受体的N‑烯丙基苯胺衍生物exo选择性的氰异丙基化芳基化反应，通过该反应可以一步合成带有三级腈结构的2‑位未取代3‑氰烷基吲哚啉。本发明首例铁催化的AIBN介导的氰烷基化反应，反应中无需加入任何的铜盐、氧化剂、碱或其它添加剂；反应呈现高度的exo选择性，该选择性以及铁盐不寻常的催化活性，可能与铁催化剂在自由基和底物之间的金属桥连作用有关。

Description

一种铁催化的氰烷基吲哚啉及其制备方法
技术领域
本发明属于化学材料技术领域，尤其涉及一种铁催化的氰烷基吲哚啉及其制备方法。
背景技术
目前，业内常用的现有技术是这样的：
吲哚化学中，吲哚啉结构要比其它相关吲哚骨架(如氧化吲哚)难合成。氧化吲哚的合成方法很多，因为它既可以通过靛红或其它相关衍生物的衍生化反应得到，也可以通过近年发展的N-芳基丙烯酰胺化学合成。相反，吲哚啉骨架的构建主要依赖于吲哚的去芳香化反应，从无环原料合成的方法则很少。或者，吲哚啉也可以通过氧化吲哚的还原反应得到，但该反应需要苛刻的反应条件，因而存在严重的官能团不耐受问题。然而，吲哚啉和氧化吲哚和芳香吲哚一样，也是广泛存在于天然产物和药物分子中的重要结构单元，它的合成也需要化学家投入更多的发明精力。另一方面，过去的十多年里，活化烯烃的双官能团化反应已被证明是快速构建多官能团化分子的强有力工具，而非活化烯烃的双官能团化反应的发明则相对少得多。
腈类化合物越来越多地被用于材料科学、药物工业和有机合成中，人们也投入了大量的努力去合成含有氰基官能团的吲哚衍生物。该领域中，大量的合成3-氰烷基氧化吲哚的方法被开发，靛红或其它氧化吲哚衍生物，以及开链的N-芳基丙烯酰胺(反应式1a2)都可以作为合成起始原料。相反，3-氰烷基吲哚啉的合成最近才被实现。去年，Brasholz课题组报道了一个光诱导的3-(2-碘乙基)吲哚与丙烯腈的自由基去芳香化环化反应，利用该反应可以得到4a-氰烷基六氢咔唑(反应式1b)。去芳香化环化反应可以一步构建具有多个手性中性的吲哚啉生物碱或拟生物碱化合物，但该策略只能用于合成2-取代的吲哚啉衍生物，且需要复杂制备的底物，非对映选择性也经常不高。更早些时候，刘国生课题组报道了多用途的Ph(OAc)2/PhI(O2Ct-Bu)2/AgF体系，使用该体系，作为活化烯烃的N-芳基丙烯酰胺，和作为非活化烯烃的N-烯丙基苯胺，都可以与乙腈发生氰烷基化/环化串联反应，分别生成含氰基的氧化吲哚和吲哚啉(反应式1c)。乙腈溶剂是理想的氰烷基化试剂，但为了活化它的C-H键，需要使用贵金属钯催化剂、过当量的AgF，和一个高碘试剂。此外，这类极性反应对腈分子中的空间位阻敏感，使用该方法不能将二级和三级腈结构片段引入到吲哚啉体系中。因此，虽然Brasholz和刘国生在该领域都做出了巨大贡献，但简单、经济，无需使用贵金属的3-氰烷基吲哚啉的合成方法仍亟待研究。
Figure BDA0001605795490000031
偶氮二异丁腈(AIBN)是高分子化学和自由基有机反应中使用最广泛的自由基引发剂之一。传统上AIBN只是用来引发自由基链式反应，自身并不参与到反应当中，因为AIBN热分解得到的异丁腈自由基空间位阻过大通常被认为没有反应活性。不过，过去的几年见证了AIBN作为三级腈源的强大能力，使用它可以构建α-位为氰基的四级碳原子中心。
发明内容
针对现有技术存在的问题，本发明提供了一种铁催化的氰烷基吲哚啉及其制备方法。本发明的发明人长期对吲哚化学和生物活性分子分析，受到这些进展的启发，推测若在将AIBN作为三级腈源的同时，将N-烯丙基酰胺的非活化烯烃部分作为自由基受体，可以开发一个制备2-位未取代3-氰烷基吲哚啉的腈烷基化/环化串联反应。
Figure BDA0001605795490000041
该反应可以解决上述存在的问题和挑战。
本发明成功实现了该合成设想。在铁催化下，N-烯丙基苯胺成功与AIBN发生exo选择的自由基氰异丙基化芳基化反应。AIBN参与的氰烷基化反应通常要在铜催化剂和/或氧化剂的作用下引发，并经常需要碱和/或一种或多种添加剂。本反应则无需铜盐、氧化剂、碱、和添加剂。此外，本发明这是首例铁催化的AIBN介导的氰烷基化反应，因为过去在此类反应中，铁盐的催化活性总是不如铜，所以从未被使用。
本发明是这样实现的，一种铁催化的氰烷基吲哚啉的制备方法，所述铁催化的氰烷基吲哚啉的制备方法包括：
使用非活化双键作为自由基受体，N-烯丙基苯胺不需要铜盐、氧化剂、碱或任何添加剂，发生氰异丙基化/环化串联反应，生成带有三级腈结构片段的3-氰烷基吲哚啉。
进一步，所述铁催化的氰烷基吲哚啉的制备方法具体包括：
步骤一，向装有磁力搅拌子的玻璃管中加入0.25mmol N-烯丙基苯胺，123mg，0.75mmol AIBN，20mg,0.05mmol Fe(NO3)3·9H2O和3.0mL DMSO；
步骤二，混合液在80℃和氩气保护下反应24h，然后用1.0mL饱和Na2S2O3和10.0mL水进行淬灭；
步骤三，10.0mL二氯甲烷萃取三次后，蒸干有机溶剂；得到的残留物以硅胶为固定相，石油醚和乙酸乙酯为洗脱剂进行柱层析，得到3-氰烷基吲哚啉。
进一步，所述的铁催化的氰烷基吲哚啉的制备方法的反应式为：
Figure BDA0001605795490000051
进一步，发生氰异丙基化/环化串联反应中，包括：
AIBN的热分解释放出一分子氮气和异丁腈自由基B；异丁腈自由基B对对N-烯丙基双键加成，生成自由基中间体C并形成一个新的C–C键；随后，苯环对分子内的自由基进行捕获，生成关环中间体D；异丁腈自由基B攫取中间体D的一个氢原子，生成吲哚啉产物2a，以及一分子异丁腈，反应完成。
进一步，发生氰异丙基化/环化串联反应的分子反应式为：
Figure BDA0001605795490000061
本发明的另一目的在于提供一种所述铁催化的氰烷基吲哚啉的制备方法制备的3-氰烷基吲哚啉。
本发明的优点及积极效果为：
本发明实现了以非活化双键作为自由基受体的N-烯丙基苯胺衍生物exo选择性的氰异丙基化芳基化反应，通过该反应可以一步合成带有三级腈结构的2-位未取代3-氰烷基吲哚啉。这也是首例铁催化的AIBN介导的氰烷基化反应，反应中无需加入任何的铜盐、氧化剂、碱或其它添加剂。反应呈现高度的exo选择性，该选择性以及铁盐不寻常的催化活性，可能与铁催化剂在自由基和底物之间的金属桥连作用有关。
附图说明
图1是本发明实施提供的铁催化的氰烷基吲哚啉的制备方法流程图。
图2是本发明实施提供的2g的二维核磁中HMBC图。
图3是本发明实施提供的2g的二维核磁中HSQC图。
图4是本发明实施提供的2g的二维核磁中COS图。
图5是本发明实施提供的GC-MS实验中有机相用GC-MS进行分析图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
下面结合附图对本发明的应用原理作进一步描述。
如图1所示，本发明实施例提供的铁催化的氰烷基吲哚啉及其制备方法包括以下步骤：
S101，向装有磁力搅拌子的玻璃管中加入N-烯丙基苯胺1(0.25mmol)，AIBN(123mg，0.75mmol)，Fe(NO3)3·9H2O(20mg,0.05mmol)和DMSO(3.0mL)；
S102，混合液在80℃和氩气保护下反应24h，然后用饱和Na2S2O3(1.0mL)和水(10.0mL)进行淬灭；
S103，二氯甲烷(10.0mL)萃取三次后，蒸干有机溶剂。得到的残留物以硅胶为固定相，石油醚和乙酸乙酯为洗脱剂进行柱层析，得到3-氰烷基吲哚啉。
下面结合表1对本发明作进一步描述。
表1.反应条件优化[a]
Figure BDA0001605795490000081
Figure BDA0001605795490000082
(a)反应条件：1a(0.25mmol)，AIBN(0.75mmol)，催化剂(0.05mmol)，氧化剂(0.5mmol)，溶剂(3.0mL)，氩气保护，80℃，24h。
(b)分离产率。
(c)5.0-6.0mol/L的癸烷溶液。
N-(2-甲基烯丙基)-N-苯基乙酰胺1a被用作模型底物进行反应条件的优化(表1)。首先对一系列的溶剂进行了筛选。结果表明，这个自由基反应中溶剂效应不明显。1a在不同的溶剂中与20mol％的CuI和3当量的AIBN作用，都以类似的产率转化为目标产物3-氰烷基吲哚啉2a(序号1-7)。这些被测试的溶剂包括甲苯、1,2-二氯乙烷(DCE)、硝基甲烷、乙腈、四氢呋喃(THF)、N,N-二甲基甲酰胺(DMF)、和二甲亚砜(DMSO)。其中，DMSO中进行的反应产率略高，为47％(序号7)。DMSO中使用其它的铜盐作为催化剂，比如CuBr、CuI、Cu(NO3)2·3H2O、和Cu(OAc)2·H2O，吲哚啉2a的产率仍较低(序号8-11)。使用AgNO3或AgOAc催化的反应则分别以46％和41％的产率生成2a(序号12和13)。这些反应中底物1a的损耗严重，可能是由于底物聚合或分解。使用FeCl3·6H2O作为催化剂，产率提高到62％(序号14)。终于，当使用廉价的Fe(NO3)3·9H2O来催化反应时，产物2a的产率为71％，勉强令人满意(序号15)。金属催化剂至关重要，因为没有催化剂时2a的产率仅有8％(序号16)。我们还将大量的氧化剂(序号17-20)、碱、配体、酸和盐(未列出)作为额外添加剂进行了测试，但产率始终都没有提高。减少催化剂和AIBN用量，以及降低反应温度到50℃，都导致产率降低(未列出)。使用更多的铁盐或AIBN，以及升温到110℃，则不能使产率进一步提高(未列出)。一些情况下，反应的再现性差，通过反复实验获得可靠数据。
下面结合表2对本发明作进一步描述。
表2.底物范围[a,b]
Figure BDA0001605795490000101
最优条件下，大量3-氰烷基吲哚啉2可以从底物1合成得到，产率最高达86％(表2)。苯环对位有一个甲基的N-(2-甲基烯丙基)乙酰苯胺衍生物与AIBN反应以83％的产率生成5-甲基吲哚啉2b。贫电子的5-溴和5-氯吲哚啉2c,d则都以中等产率生成。带有邻位取代基的烯丙基化乙酰苯胺被证明是挑战性的底物，由于空间位阻的影响，对应的7-氯吲哚啉2e仅以21％的产率生成。间位被氯原子取代的底物反应时存在区域选择性问题，对应产物4-氯吲哚啉2f和6-氯吲哚啉2f'分别以40％和28％的产率生成。接下来本发明发明了吸电子N-保护基的范围。丙酰基保护的5-甲基和5-氯吲哚啉2g,h分别以74％和60％的产率生成。长链保护基，如辛酰基、癸酰基、十二烷酰基和硬脂酰基等，在反应中都可以被兼容，没有观察到明显的位阻效应，对应3-氰烷基产物2i-p中等或高产率地生成。而在底物合成中，这些保护基的位阻效应巨大，导致本发明不得不改变底物合成方法。
拥有最长保护链的N-硬脂酰基吲哚啉2p的产率最高，可能是由于保护基的位阻抑制了底物聚合。4-氨基吡啶合成得到的杂环芳基底物也可以参与反应，生成对应的2,3-二氢吡咯[3,2-c]并吡啶2m，虽然产率不高。可能由于自由基的反应活性过高，苯甲酰基保护的烯丙基苯胺参与的反应较为复杂，本发明无法从其中分离得到纯净产物。接下来本发明将该反应拓展到了磺酰基保护的烯丙基苯胺。N-芳基磺酰基和N-烷基磺酰基吲哚啉2q-s都仅以较低的产率生成。通过产物N-邻甲苯磺酰基吲哚啉2r的核磁数据判断，在生成N-芳基磺酰基吲哚啉2q,r的反应中，是N-芳基而非芳基磺酰基参与到关环步骤中。最后，将该反应进一步拓展到偶氮二异丁酸二甲酯(MAIB)的尝试没有成功。
根据鲍德温规则(Baldwin'srule)，5-exo-trig、6-exo-trig和6-endo-trig都是有利的成环方式。因此，本发明起初都使用2-甲基烯丙基溴来合成底物，以尽力避免潜在竞争的形式上(formal)6-endo-trig环化反应。在以上所有反应中均实现了很好的exo选择性之后，本发明想知道使用简单烯丙基溴合成的底物能否用于本反应。理论上分析，因为自由基高度活泼，而无官能团稳定的一级和二级C-自由基的稳定性相差又不大，该氰烷基化/环化串联反应按exo和endo两种方式应该都可以进行。当N-烯丙基-N-对溴苯基乙酰胺在最优条件下反应时，5-exo-trig产物2t专一地生成，没有检测到形式上的6-endo-trig产物(反应式2)。根据黄汉民的发明，本发明推测这个exo选择性以及铁催化剂特殊的活性，可能是由于催化剂与自由基和底物形成了类似A这样的配合物，其中的金属桥连可能对反应起到活化和导向作用。
Figure BDA0001605795490000121
为了验证本反应的自由基属性，本发明开展了一些对照实验(反应式3a)。和预料的一样，当加入1.2当量的四甲基哌啶氮氧化物(TEMPO)或2当量的2,6-二叔丁基-4-甲基苯酚(BHT)作为自由基抑制剂时，最优条件下的模型反应几乎被完全抑制。此外，BHT实验中，氰异丙基-BHT加合物通过气相色谱-质谱联用(GC-MS)检测到，该结果验证了氰异丙基自由基B的生成。
根据以上结果和一些前期报道，本发明提出了一个可能的反应机理(反应式3b)。一开始，AIBN的热分解释放出一分子氮气和异丁腈自由基B。异丁腈自由基B对对N-烯丙基双键加成，生成自由基中间体C并形成一个新的C–C键。类似A配合物中铁离子对自由基和底物的桥连可能对这个过程有促进和导向作用。随后，苯环对分子内的自由基进行捕获，生成关环中间体D。异丁腈自由基B攫取中间体D的一个氢原子，生成吲哚啉产物2a，以及一分子异丁腈，反应完成。
Figure BDA0001605795490000131
下面结合具体分析对本发明作进一步描述。
商业购买的化学试剂均未经特殊处理直接使用。反应过程通过薄层色谱(TLC)在F254玻璃硅胶板上进行监测。产物通过加压柱层析使用300-400目硅胶进行分离提纯。1H、13C、DEPT和2D NMR使用布鲁克AscendTM 400核磁共振仪在25℃进行测试，TMS作为内标。高分辨质谱(HRMS)在布鲁克microTOF II Focus质谱仪(ESI)上进行。使用安捷伦7890A/5975C气相色谱质谱联用仪(GC-MS)对部分反应混合液进行分析。底物1n-p从4-甲基-N-(2-甲基烯丙基)苯胺和对应酰氯合成，其它底物则从酰基苯胺和2-甲基烯丙基溴或烯丙基溴合成。
下面结合产物光谱数据对本发明作进一步描述。
1、产物光谱数据
Figure BDA0001605795490000141
2a,3-(1-acetyl-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.13(s,3H),1.43(s,3H),1.51(s,3H),1.88(d,J＝14.9Hz,1H),2.07(d,J＝14.9Hz,1H),2.27(s,3H),3.85(d,J＝10.8Hz,1H),4.40(d,J＝10.8Hz,1H),7.05(dd,J＝7.4,7.3Hz,1H),7.12(d,J＝7.0Hz,1H),7.22-7.26(m,1H),8.22(d,J＝8.1Hz,1H)；13C NMR(100MHz,CDCl3)δ＝168.94,141.83,138.55,128.54,125.22,123.84,122.33,117.23,60.64,50.96,43.62,30.48,30.39,28.39,27.69,24.33；HRMS(ESI-TOF)Calcd for C16H21N2O+([M+H]+)257.1648.Found 257.1651.
Figure BDA0001605795490000142
2b,3-(1-acetyl-3,5-dimethylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.15(s,3H),1.44(s,3H),1.50(s,3H),1.86(d,J＝14.8Hz,1H),2.06(d,J＝14.8Hz,1H),2.25(s,3H),2.32(s,3H),3.84(d,J＝10.8Hz,1H),4.36(d,J＝10.8Hz,1H),6.92(s,1H),7.04(d,J＝7.5Hz,1H),8.08(d,J＝8.2Hz,1H)；13CNMR(100MHz,CDCl3)δ＝168.60,139.49,138.78,133.49,128.99,125.28,122.87,116.94,60.84,50.89,43.60,30.50,30.36,28.20,27.73,24.24,21.14；HRMS(ESI-TOF)Calcd forC17H23N2O+([M+H]+)271.1805.Found 271.1804.
Figure BDA0001605795490000143
2c,3-(1-acetyl-5-bromo-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝1.15(s,3H),1.46(s,3H),1.50(s,3H),1.87(d,J＝14.9Hz,1H),2.05(d,J＝14.9Hz,1H),2.25(s,3H),3.86(d,J＝10.9Hz,1H),4.42(d,J＝10.9Hz,1H),7.21(d,J＝1.9Hz,1H),7.34(dd,J＝2.0,8.6Hz,1H),8.10(d,J＝8.6,1H)；13C NMR(100MHz,CDCl3)δ＝169.00,140.97,140.94,131.39,125.55,125.02,118.67,116.12,60.57,50.81,43.69,30.43,30.36,28.36,27.82,24.21；HRMS(ESI-TOF)Calcd for C16H20BrN2O+([M+H]+)335.0754.Found 335.0756.
Figure BDA0001605795490000151
2d,3-(1-acetyl-5-chloro-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝1.15(s,3H),1.46(s,3H),1.51(s,3H),1.87(d,J＝14.9Hz,1H),2.05(d,J＝14.9Hz,1H),2.26(s,3H),3.87(d,J＝10.9Hz,1H),4.43(d,J＝10.9Hz,1H),7.07(d,J＝2.0Hz,1H),7.20(dd,J＝2.2,8.6Hz,1H),8.16(d,J＝8.6,1H)；13C NMR(100MHz,CDCl3)δ＝168.94,140.58,140.47,128.70,128.47,125.02,122.64,118.23,60.61,50.78,43.70,30.43,30.37,28.36,27.80,24.18；HRMS(ESI-TOF)Calcd for C16H20ClN2O+([M+H]+)291.1259.Found 291.1273.
Figure BDA0001605795490000152
2e,3-(1-acetyl-7-chloro-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.38(s,3H),1.40(s,3H),1.51(s,3H),1.77(d,J＝14.9Hz,1H),2.03(d,J＝14.9Hz,1H),2.33(s,3H),3.99(d,J＝11.1Hz,1H),4.29(d,J＝11.1Hz,1H),7.08-7.14(m,2H),7.24-7.29(m,1H)；13C NMR(100MHz,CDCl3)δ＝170.17,145.38,139.36,129.78,126.55,125.15,124.29,121.00,63.42,48.27,45.42,30.44,29.94,28.15,24.19,23.40；HRMS(ESI-TOF)Calcd forC16H20ClN2O+([M+H]+)291.1259.Found 291.1257.
Figure BDA0001605795490000153
2f,3-(1-acetyl-4-chloro-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝0.99(s,3H),1.44(s,3H),1.66(s,3H),2.10(d,J＝15.0Hz,1H),2.27(s,3H),2.30(d,J＝15.0Hz,1H),3.80(d,J＝11.1Hz,1H),4.58(d,J＝11.1Hz,1H),6.97(dd,J＝0.5,8.0Hz,1H),7.19(dd,J＝8.1,8.1Hz,1H),8.25(d,J＝8.1Hz,1H)；13C NMR(100MHz,CDCl3)δ＝169.19,144.47,132.94,130.32,130.09,125.36,125.11,115.92,60.40,47.59,44.84,30.71,30.40,27.63,26.34,24.50；HRMS(ESI-TOF)Calcd for C16H20ClN2O+([M+H]+)291.1259.Found 291.1257.
Figure BDA0001605795490000161
2f',3-(1-acetyl-6-chloro-3-methylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.14(s,3H),1.44(s,3H),1.49(s,3H),1.86(d,J＝13.9Hz,1H),2.05(d,J＝13.9Hz,1H),2.26(s,3H),3.86(d,J＝10.8Hz,1H),4.42(d,J＝10.8Hz,1H),7.02(s,2H),8.27(s,1H)；13C NMR(100MHz,CDCl3)δ＝169.10,142.81,137.03,134.14,125.05,123.81,123.07,117.51,60.87,50.86,43.37,30.43,30.38,28.49,27.78,24.25；HRMS(ESI-TOF)Calcd for C16H20ClN2O+([M+H]+)291.1259.Found 291.1259.
Figure BDA0001605795490000162
2g,3-(3,5-dimethyl-1-propionylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.17(s,3H),1.22(t,J＝7.4Hz,3H),1.44(s,3H),1.50(s,3H),1.86(d,J＝14.9Hz,1H),2.06(d,J＝14.8Hz,1H),2.32(s,3H),2.37-2.57(m,2H),3.82(d,J＝10.8Hz,1H),4.35(d,J＝10.8Hz,1H),6.91(s,1H),7.04(d,J＝7.9Hz,1H),8.12(d,J＝8.2Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.91,139.68,138.73,133.31,128.99,125.30,122.81,116.89,59.92,50.82,43.62,30.50,30.30,29.11,28.13,27.83,21.11,8.65；HRMS(ESI-TOF)Calcd for C18H25N2O+([M+H]+)285.1961.Found 285.1943.
Figure BDA0001605795490000171
2h,3-(5-chloro-3-methyl-1-propionylindolin-3-yl)-2,2-dimethylpropanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.17(s,3H),1.22(t,J＝7.4Hz,3H),1.46(s,3H),1.50(s,3H),1.87(d,J＝14.9Hz,1H),2.05(d,J＝14.9Hz,1H),2.40-2.58(m,2H),3.85(d,J＝10.8Hz,1H),4.42(d,J＝10.8Hz,1H),7.07(s,1H),7.20(dd,J＝2.1,8.6Hz,1H),8.19(d,J＝8.6Hz,1H)；13C NMR(100MHz,CDCl3)δ＝172.26,140.65,140.53,128.51,128.46,125.05,122.59,118.14,59.71,50.69,43.72,30.43,30.32,29.12,28.31,27.88,8.53；HRMS(ESI-TOF)Calcd for C17H22ClN2O+([M+H]+)305.1415.Found 305.1418.
Figure BDA0001605795490000172
2i,2,2-dimethyl-3-(3-methyl-1-octanoylindolin-3-yl)propanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝6.5Hz,3H),1.17(s,3H),1.27-1.39(m,8H),1.43(s,3H),1.50(s,3H),1.70-1.77(m,2H),1.88(d,J＝14.8Hz,1H),2.07(d,J＝14.8Hz,1H),2.38-2.53(m,2H),3.84(d,J＝10.8Hz,1H),4.37(d,J＝10.8Hz,1H),7.04(dd,J＝7.3,7.4Hz,1H),7.12(d,J＝7.3Hz,1H),7.24(dd,J＝7.6,7.6Hz,1H),8.25(d,J＝8.0Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.71,141.99,138.59,128.51,125.24,123.69,122.26,117.25,59.96,50.80,43.62,36.03,31.74,30.47,30.29,29.35,29.19,28.19,27.85,24.52,22.64,14.10；HRMS(ESI-TOF)Calcd for C22H33N2O+([M+H]+)341.2587.Found341.2590.
Figure BDA0001605795490000173
2j,3-(3,5-dimethyl-1-octanoylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝7.0Hz,3H),1.19(s,3H),1.27-1.40(m,8H),1.44(s,3H),1.50(s,3H),1.69-1.76(m,2H),1.86(d,J＝14.8Hz,1H),2.06(d,J＝14.8Hz,1H),2.32(s,3H),2.37-2.51(m,2H),3.83(d,J＝10.8Hz,1H),4.34(d,J＝10.8Hz,1H),6.91(s,1H),7.02-7.05(m,1H),8.12(d,J＝8.2Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.36,139.65,138.80,133.31,128.94,125.29,122.82,116.96,60.16,50.75,43.60,35.91,31.74,30.48,30.26,29.35,29.19,28.01,27.88,24.56,22.64,21.11,14.10；HRMS(ESI-TOF)Calcd for C23H35N2O+([M+H]+)355.2744.Found355.2759.
Figure BDA0001605795490000181
2k,3-(5-bromo-3-methyl-1-octanoylindolin-3-yl)-2,2-dimethylpropanenitrile,white solid:mp 119-120℃.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝6.9Hz,3H),1.19(s,3H),1.26-1.40(m,8H),1.46(s,3H),1.50(s,3H),1.68-1.76(m,2H),1.87(d,J＝14.8Hz,1H),2.04(d,J＝14.8Hz,1H),2.37-2.52(m,2H),3.86(d,J＝10.8Hz,1H),4.40(d,J＝10.8Hz,1H),7.21(s,1H),7.33(dd,J＝2.0,8.6Hz,1H),8.14(d,J＝8.6Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.78,141.09,141.00,131.34,125.48,125.03,118.68,115.92,59.88,50.65,43.70,35.90,31.71,30.41,30.28,29.29,29.16,28.20,27.96,24.41,22.63,14.10；HRMS(ESI-TOF)Calcd for C22H32BrN2O+([M+H]+)419.1693.Found 419.1697.
Figure BDA0001605795490000182
2l,3-(5-chloro-3-methyl-1-octanoylindolin-3-yl)-2,2-dimethylpropanenitrile,white crystal:mp 106-107℃.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝7.0Hz,3H),1.18(s,3H),1.26-1.40(m,8H),1.46(s,3H),1.50(s,3H),1.69-1.76(m,2H),1.87(d,J＝14.8Hz,1H),2.04(d,J＝14.8Hz,1H),2.37-2.52(m,2H),3.86(d,J＝10.8Hz,1H),4.41(d,J＝10.8Hz,1H),7.07(d,J＝1.7Hz,1H),7.19(dd,J＝2.2,8.6Hz,1H),8.19(d,J＝8.6Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.71,140.61,128.50,128.42,125.04,122.58,118.22,59.93,50.62,43.70,35.87,31.72,30.41,30.28,29.29,29.16,28.19,27.94,24.42,22.63,14.10；HRMS(ESI-TOF)Calcd for C22H32ClN2O+([M+H]+)375.2198.Found 375.2199.
Figure BDA0001605795490000183
2m,2,2-dimethyl-3-(3-methyl-1-octanoyl-2,3-dihydro-1H-pyrrolo[3,2-c]pyridin-3-yl)propanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝0.89(t,J＝7.0Hz,3H),1.18(s,3H),1.27-1.40(m,8H),1.48(s,3H),1.56(s,3H),1.68-1.75(m,2H),1.95(d,J＝14.9Hz,1H),2.13(d,J＝14.9Hz,1H),2.40-2.55(m,2H),3.89(d,J＝10.8Hz,1H),4.44(d,J＝10.8Hz,1H),8.06(d,J＝2.8Hz,1H),8.34(s,1H),8.43(d,J＝4.9Hz,1H)；13C NMR(100MHz,CDCl3)δ＝172.76,150.38,148.56,144.23,134.04,124.95,111.54,60.00,50.83,43.02,36.10,31.71,30.40,30.33,29.21,29.15,28.66,28.10,24.15,22.64,14.11；HRMS(ESI-TOF)Calcd for C21H32N3O+([M+H]+)342.2540.Found 342.2537.
Figure BDA0001605795490000191
2n,3-(1-decanoyl-3,5-dimethylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝7.0Hz,3H),1.19(s,3H),1.25-1.38(m,12H),1.44(s,3H),1.50(s,3H),1.69-1.76(m,2H),1.86(d,J＝14.8Hz,1H),2.05(d,J＝14.8Hz,1H),2.32(s,3H),2.37-2.51(m,2H),3.83(d,J＝10.8Hz,1H),4.34(d,J＝10.8Hz,1H),6.91(s,1H),7.03(dd,J＝0.9,8.1Hz,1H),8.12(d,J＝8.2Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.38,139.64,138.81,133.32,128.96,125.29,122.80,116.98,60.18,50.75,43.61,35.93,31.90,30.48,30.27,29.54,29.50,29.41,29.30,27.98,27.90,24.57,22.68,21.11,14.12；HRMS(ESI-TOF)Calcd for C25H39N2O+([M+H]+)383.3057.Found 383.3052.
Figure BDA0001605795490000192
2o,3-(1-dodecanoyl-3,5-dimethylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝6.9Hz,3H),1.19(s,3H),1.25-1.39(m,16H),1.44(s,3H),1.50(s,3H),1.69-1.76(m,2H),1.86(d,J＝14.8Hz,1H),2.06(d,J＝14.8Hz,1H),2.32(s,3H),2.38-2.51(m,2H),3.83(d,J＝10.8Hz,1H),4.34(d,J＝10.8Hz,1H),6.91(s,1H),7.03(d,J＝8.0Hz,1H),8.12(d,J＝8.2Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.38,139.64,138.81,133.32,128.96,125.29,122.80,116.97,60.17,50.75,43.61,35.93,31.92,30.48,30.26,29.64,29.54,29.41,29.35,27.98,27.90,24.57,22.70,21.11,14.13；HRMS(ESI-TOF)Calcd for C27H43N2O+([M+H]+)411.3370.Found 411.3374.
Figure BDA0001605795490000193
2p,3-(3,5-dimethyl-1-stearoylindolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝0.88(t,J＝7.0Hz,3H),1.19(s,3H),1.24-1.38(m,28H),1.44(s,3H),1.50(s,3H),1.69-1.76(m,2H),1.86(d,J＝14.8Hz,1H),2.05(d,J＝14.8Hz,1H),2.32(s,3H),2.36-2.51(m,2H),3.83(d,J＝10.8Hz,1H),4.34(d,J＝10.8Hz,1H),6.91(s,1H),7.03(d,J＝7.5Hz,1H),8.12(d,J＝8.2Hz,1H)；13C NMR(100MHz,CDCl3)δ＝171.38,139.64,138.81,133.32,128.96,125.29,122.80,116.97,60.18,50.75,43.61,35.93,31.94,30.48,30.27,29.71,29.67,29.55,29.42,29.37,27.98,27.90,24.57,22.70,21.11,14.13；HRMS(ESI-TOF)Calcd forC33H55N2O+([M+H]+)495.4309.Found 495.4311.
Figure BDA0001605795490000201
2q,2,2-dimethyl-3-(3-methyl-1-(phenylsulfonyl)indolin-3-yl)propanenitrile,colorless oil.1H NMR(400MHz,CDCl3)δ＝1.19(s,3H),1.29(s,3H),1.30(s,3H),1.59(d,J＝14.9Hz,1H),1.94(d,J＝14.9Hz,1H),3.70(d,J＝10.8Hz,1H),4.04(d,J＝10.8Hz,1H),7.01-7.08(m,2H),7.24(ddd,J＝1.6,7.2,7.2Hz,1H),7.45-7.50(m,2H),7.57(dddd,J＝1.2,1.2,7.5,7.4Hz,1H),7.69(d,J＝8.1Hz,1H),7.84-7.87(m,2H)；13C NMR(100MHz,CDCl3)δ＝140.32,139.34,136.82,133.38,129.20,128.62,127.34,125.16,123.97,123.08,114.71,61.64,49.54,43.70,30.37,29.85,27.48,26.66；HRMS(ESI-TOF)Calcd for C20H23N2O2S+([M+H]+)355.1475.Found 355.1471.
Figure BDA0001605795490000202
2r,3-(3,5-dimethyl-1-(o-tolylsulfonyl)indolin-3-yl)-2,2-dimethylpropanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝1.27(s,3H),1.34(s,3H),1.40(s,3H),1.64(d,J＝14.9Hz,1H),1.99(d,J＝14.9Hz,1H),2.30(s,3H),2.60(s,3H),3.74(d,J＝10.7Hz,1H),4.03(d,J＝10.7Hz,1H),6.92(s,1H),6.97-7.00(m,1H),7.29-7.34(m,3H),7.45(ddd,J＝1.3,7.6,7.4Hz,1H),7.96(d,J＝8.0Hz,1H)；13C NMR(100MHz,CDCl3)δ＝139.53,138.53,138.17,137.22,133.49,133.12,132.98,129.54,128.98,126.40,125.27,123.59,114.62,61.81,49.61,43.98,30.38,30.07,27.39,25.73,21.08,21.05；HRMS(ESI-TOF)Calcd for C22H27N2O2S+([M+H]+)383.1788.Found 383.1789.
Figure BDA0001605795490000211
2s,2,2-dimethyl-3-(3-methyl-1-(methylsulfonyl)-5-phenylindolin-3-yl)propanenitrile,pale yellow oil.1H NMR(400MHz,CDCl3)δ＝1.39(s,3H),1.42(s,3H),1.61(s,3H),1.95(d,J＝14.9Hz,1H),2.18(d,J＝14.9Hz,1H),2.98(s,3H),3.81(d,J＝10.2Hz,1H),4.13(d,J＝10.2Hz,1H),7.34(dddd,J＝1.2,1.2,7.4,7.3Hz,1H),7.40-7.47(m,5H),7.53-7.56(m,2H)；13C NMR(100MHz,CDCl3)δ＝140.45,140.01,139.31,137.25,128.90,127.83,127.32,126.90,125.14,122.25,113.52,62.64,49.64,43.82,35.08,30.48,29.97,28.01,26.85；HRMS(ESI-TOF)Calcd for C21H25N2O2S+([M+H]+)369.1631.Found 369.1631.
Figure BDA0001605795490000212
2t,3-(1-acetyl-5-bromoindolin-3-yl)-2,2-dimethylpropanenitrile,paleyellow oil.1H NMR(400MHz,CDCl3)δ＝1.47(s,3H),1.51(s,3H),1.97(d,J＝6.3Hz,2H),2.25(s,3H),3.58-3.66(m,1H),4.00(dd,J＝6.7,10.7Hz,1H),4.39(dd,J＝9.6,10.5Hz,1H),7.24(s,1H),7.34(ddd,J＝0.6,2.0,8.6Hz,1H),8.10(d,J＝8.6Hz,1H)；13C NMR(100MHz,CDCl3)δ＝168.80,141.55,136.21,131.29,126.55,124.71,118.44,116.11,55.72,47.26,37.26,31.43,28.20,26.27,24.19；HRMS(ESI-TOF)Calcd for C15H18BrN2O+([M+H]+)321.0597.Found 321.0599.
下面结合二维核磁图对本发明作进一步描述。
2g的二维核磁中，图2是本发明实施提供的2g的二维核磁中HMBC图。
图3是本发明实施提供的2g的二维核磁中HSQC图。
图4是本发明实施提供的2g的二维核磁中COS图。
下面结合GC-MS实验对本发明作进一步描述。
GC-MS实验
最优条件下的模型反应中加入2.0当量的2,6-二叔丁基-4-甲基苯酚(BHT)，得到的混合液反应12h后用饱和Na2S2O3(1.0mL)和水(10.0mL)进行淬灭。二氯甲烷(10.0mL)萃取三次后，有机相用GC-MS进行分析。如图5。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (1)

1.一种铁催化的氰烷基吲哚啉的制备方法，其特征在于，所述铁催化的氰烷基吲哚啉的制备方法包括：
步骤一，向装有磁力搅拌子的玻璃管中加入0.25mmol N-烯丙基苯胺类化合物1a，123mg，0.75mmolAIBN，20mg,0.05mmol Fe(NO3)3·9H2O和3.0mL DMSO；
步骤二，混合液在80℃和氩气保护下反应24h，然后用1.0mL饱和Na2S2O3和10.0mL水进行淬灭；
步骤三，10.0mL二氯甲烷萃取三次后，蒸干有机溶剂；得到的残留物以硅胶为固定相，石油醚和乙酸乙酯为洗脱剂进行柱层析，得到3-氰烷基吲哚啉类化合物2a；
Figure FDA0002963842870000011
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