CN110028403A - 一种合成丁二酸类化合物的方法 - Google Patents

一种合成丁二酸类化合物的方法 Download PDF

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CN110028403A
CN110028403A CN201910319124.9A CN201910319124A CN110028403A CN 110028403 A CN110028403 A CN 110028403A CN 201910319124 A CN201910319124 A CN 201910319124A CN 110028403 A CN110028403 A CN 110028403A
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余达刚
李静
鞠涛
周榆钦
付强
叶剑衡
廖黎丽
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Sichuan University
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Abstract

本发明提供了一种合成丁二酸类化合物的方法，具体的为：在反应管中加入底物、光催化剂和碱，再在CO2的气氛下加入还原剂和溶剂，在可见光照射下进行反应，原料反应完后，进行淬灭处理，之后进行分离纯化，即得烯烃的双羧基化产物丁二酸类化合物；光催化剂为4CzIPN或Ir[(ppy)2(dtbppy)]PF6等；反应底物包括1,1‑二芳基乙烯、单芳基取代烯烃化合物、丙烯酸酯类化合物和联烯。本发明方案的反应条件温和，反应底物适用性广，且在放大至克级规模的情况下，产率也基本不受影响；同时本发明克服了现有技术中试剂毒性高、反应条件苛刻的缺陷，具有良好的工业应用前景。

Description

一种合成丁二酸类化合物的方法
技术领域
本发明属于有机合成技术领域，具体涉及一种合成丁二酸类化合物的方法。
背景技术
丁二酸类化合物广泛存在于天然分子、药物和材料分子中。现有技术中利用CO2合成丁二酸类化合物的方法可分为碱金属还原烯烃捕获CO2、电解活化的烯烃和CO2、传统方法的水解β-氰基羧酸。
碱金属还原烯烃捕获CO2法是采用碱金属作为还原剂来直接还原烯烃，再与CO2发生反应，从而合成丁二酸类化合物。该反应使用了钠、钾作为直接的还原剂，这种极强的还原性条件使得反应物几乎不能带有除了烷基取代基以外的任何基团，这使得反应的底物普适性受到了极大的限制。
电解活化的烯烃和CO2法是通过电化学方法实现烯烃的双羧基化反应。烯烃和二氧化碳都可以在阴极得到电子，变成烯基自由基负离子和二氧化碳自由基负离子，再发生后续的反应，得到丁二酸类化合物。现有技术中公开了一种在电解池中加入镍催化剂以实现电化学与金属有机结合的烯烃的双羧基化反应的技术，但产率依然不高。
工业上合成丁二酸类化合物普遍采用电化学方法和水解腈的方法。电化学反应直接通过阴极给电子来还原烯烃或者二氧化碳，实现对丁二酸类化合物的合成。但是活化烯烃或者CO2的还原电势较高，很多官能团在该条件下会被优先还原，因此该方法的底物普适性不高，反应选择性较差。水解腈的方法则需要高温和酸性水溶液条件，能耗高，设备要求高，同时会产生大量酸性废水，对环境有较大影响；此外，所需要氰化钠、氰化钾等原料具有较大毒性。
光化学方面，有通过自由基前体原位生成的高活性自由基与烯烃加成后生成苄基自由基中间体，之后将该中间体还原为苄基碳负离子，再与CO2反应完成杂羧化反应；也有通过光/金属协调催化来实现烯烃的选择性氢羧化反应。但通过可见光催化，在温和的反应条件下实现两分子CO2对烯烃的插入，一次性构建两个C-C键还存在着较大的困难。此外，由于烯烃的还原电势较高，通过可见光促进的烯烃单电子还原来实现烯烃的双官能团化的反应还未被报导。最后，该反应同样还面临着化学选择性的问题，如何高选择性的生成双羧基化的产物，避免氢羧基化副产物的生成。因此由可见光催化还原烯烃实现的双羧基化目前面临诸多的困难与挑战。
发明内容
针对现有技术的缺点，本发明的目的在于提供一种丁二酸类化合物(包含丁二酸结构的化合物)的合成方法，该方法能够合成其它方法很难合成的丁二酸类化合物，产率高、反应条件温和、反应试剂毒性低、成本低。
为了达到上述目的，本发明所采用的技术方案是：提供一种合成丁二酸类化合物的方法，方法具体为：
将底物、光催化剂和碱按1:0.005～0.5:1～20的摩尔比加入反应容器中，然后在CO2气氛下加入还原剂和溶剂，所加入的还原剂与底物的摩尔比为1～20:1；再在室温下搅拌反应2～48h，反应过程中用波长为400～550nm的可见光照射反应液；然后用2N的稀盐酸淬灭反应，再对反应后的混合物进行分离纯化，得丁二酸类化合物；
底物为1,1-二芳基乙烯类化合物(Ⅰ)、单芳基取代烯烃类化合物(Ⅱ)、丙烯酸酯类化合物(III)或4-(丁-2,3-二烯-2-基)-1,1'-联苯(IV)；
其中，R1为氢原子、烷基或卤原子；R2为氢原子、芳基、取代芳基、烷基、取代烷基、烃氧基、巯基、羟基、酯基或卤原子；R3为氢原子或烷基；R4为氢原子或烷基；R5和R6为烃基；
光催化剂为4CzIPN、Ir[(ppy)2(dtbppy)]PF6、Ir[dF(CF3)ppy]2(dtbbpy)PF6、fac-Ir(ppy)3或Ru(bpz)3(PF6)2；
碱为Cs2CO3、LiOtBu、NaOtBu、KOtBu、Na2CO3、K2CO3或CsF；
还原剂为TMEDA、HEH、iPr2NEt或Et3N；
溶剂为极性溶剂。
本发明用TMEDA、HEH、iPr2NEt或Et3N等还原剂替代还原性很强的钠、钾等金属，反应条件相对温和，而且对底物的限制较低，即使底物带有芳基等基团也能正常进行反应，并且只会对烯键进行还原，而不影响其他基团，可以合成具有特殊结构的丁二酸类化合物，扩展了丁二酸类化合物的数量，并可以为药物合成等提供新思路和中间体。
本发明在反应过程中用490～550nm的可见光照射反应物，该波长范围内的光为蓝光，蓝光的能量较低，仅仅对光催化剂起作用，而且该波长范围的光更容易被光催化剂吸收，可高效活化光催化剂，提高反应效率；另外蓝光不会被有机化合物吸收，也就不会引起化合物的分解，保证了合成反应具有较高的产率。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，光催化剂优选为4CzIPN，碱优选为Cs2CO3，底物、光催化剂和碱的摩尔比为1:0.02:4.5。
进一步，还原剂优选为iPr2NEt，其与底物的摩尔比为1:1。
进一步，溶剂为DMF、DMA、DMSO、NMP、MeCN、1,4-dioxane和MeOH中的至少一种。
进一步，反应过程中用波长为450nm的可见光照射反应物。
进一步，搅拌反应时间为24h。
本发明的有益效果是：本发明可以在可见光诱导、CO2参与下高效的合成丁二酸类化合物；本发明方案的反应条件温和，反应底物选择性广，且可放大至克级规模，产率也基本不受影响；本发明克服了现有技术试剂毒性高、反应条件苛刻的缺陷，具有良好的工业应用前景。
附图说明
图1为本发明中丁二酸类化合物的合成机理图。
具体实施方式
下面结合实施例对本发明的具体实施方式做详细的说明。
实施例一
一种合成丁二酸类化合物的方法，包括以下步骤：
(1)向含有磁子的干燥的Schlenk管(25mL)中加入0.2mmol的反应底物(反应底物如表1～表4所示)和0.004mmol的光催化剂4CzIPN(4mg，2mol％)；
(2)将Schlenk管转入手套箱中，并向Schlenk管中装入0.9mmol的Cs2CO3(294mg，0.9mmol，4.5倍当量)；
(3)将Schlenk管封闭后从手套箱中取出并连接到连有CO2钢瓶的双排管上，拧松盖子并在双排管上抽充CO2至少3次，排除管中的N2，使其管中充满CO2气体(CO2 1atm)；
(4)向充有CO2的Schlenk管中加入1mL溶剂DMF和0.2mmol的还原剂iPr2NEt(34μL，1倍当量)；
(5)将装有反应液的Schlenk管置于距30W蓝色LED灯(波长为450nm左右)1～2cm处，在室温(25℃左右)下搅拌反应24小时；
(6)用1mL水、2mL乙酸乙酯和2mL盐酸配成酸淬灭剂，用酸淬灭剂淬灭反应；
(7)将淬灭后的反应物置于旋转蒸发器中浓缩旋干，残余物通过快速柱层析纯化，纯化条件为：先用石油醚/乙酸乙酯＝6/1(v/v)的混合液冲洗，然后用石油醚/乙酸乙酯＝2/1(v/v)并加0.2～0.3％冰醋酸的混合溶液冲洗，最后用石油醚/乙酸乙酯＝1/1(v/v)并加0.2～0.3％冰醋酸的混合溶液洗脱，得到纯的产物。
表1以1,1-二芳基乙烯类化合物为底物及其所对应的产物以及产率
表2以单芳基取代烯烃类化合物为底物及其所对应的产物以及产率
表3以丙烯酸酯类化合物为底物及其所对应的产物以及产率
表4以联烯4-(丁-2,3-二烯-2-基)-1,1'-联苯为底物及其所对应的产物以及产率
实施例二
以1,1-二苯基乙烯为底物，合成丁二酸类化合物，反应方程式如式V所示，合成步骤同实施例一，并且以实施例一中的反应条件为标准反应条件，在标准条件的基础上对反应条件进行调节，并统计相应产物的产率，结果列于表5。
表5反应条件的改变对产率的影响
注：表中标准反应条件为：底物0.2mmol，光催化剂4CzIPN 0.004mmol，碱Cs2CO30.9mmol，还原剂iPr2NEt 0.2mmol，溶剂DMF 1mL，1atm CO2，30W蓝光照射，室温，24小时；N.D.为未检测到产物，HEH为汉斯酯(Hantzsch ester)，DMF为N,N-二甲基甲酰胺，DMA为N,N-二甲基乙酰胺。
从表5可以看出，光催化剂、可见光、还原剂和碱对于本发明中的合成是必不可少的。例如，在对不同光催化剂的筛选中发现，有机染料4CzIPN(激发态Ered＝+1.35V vs SCE)比其他光催化剂(如Ir[dF(CF3)ppy]2(dtbbpy)PF6)显示出了更高的活性，可得到最高的产率。除了Ir[dF(CF3)ppy]2(dtbbpy)PF6和4CzIPN之外，发明人还考察了其它不同的光催化剂如Ir[(ppy)2(dtbppy)]PF6，发现的产率可达40％，不过催化剂替换为fac-Ir(ppy)3后收率仅有35％。
结果分析
按照式V中的方程式进行反应，首先在不加CO2的环境下进行实验，得到了15％的还原产物(表5，编号2)，而不能得到丁二酸类化合物；按照式VI中的方程式进行反应，将化合物1ab按照实施例二中的标准反应条件进行合成，主要得到了脱氟羧基化和双羧化产物2ab'和2a，它们可能由相应阴离子发生β-F消除产生；其次，在不加CO2的情况下观察3p化合物是否能被还原，结果产生16％的还原开环产物4p；最后，当加入氘代甲醇作为质子源时，反应得到还原产物2a'和自由基偶联产物2a”，产率分别为41％和28％。这些结果有力地表明烯烃的阴离子自由基是该反应中的重要中间体。
此外，按照式VII中的方程式进行自由基抑制试验，当在反应体系中加入三个当量的自由基捕获剂如2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)、4-甲基-2,6-二叔丁基苯酚(BHT)、二苯基二硒醚(PhSe-SePh)，只产生痕量甚至不产生目标产物4e，这说明该反应可能包含自由基过程。由于在反应体系中未检测到α-氢羧化产物，但得到了TEMPO与3e先被还原捕获二氧化碳再与苄位偶联的加和物。这些结果表明苄基自由基也可能是合成过程中的活性中间体。
此外，反应物1d在CO2氛围中加入D2O后可获得苄位氘代产物5(式VIII)，这表明在合成过程中可能产生苄基自由基阴离子。
基于上述机理研究，提出了一种可能的反应机理，如图1所示。有机小分子光催化剂4CzIPN受光激发产生*4CzIPN的激发单重态，然后经历SET与iPr2NEt以提供强还原剂4CzIPN·-，该中间体对碳碳双键有特殊的反应性，可以选择性地对活化的碳碳双键进行还原。然后，4CzIPN·-将烯烃1还原为其对应的自由基阴离子A，A可以与CO2反应生成中间体B(图1路径a)。中间体B然后与另一分子4CzIPN·-再发生一次SET生成苯基阴离子C，最后与第二分子CO2反应，淬灭反应后即得到所需的产物2。值得注意的是，化合物1的自由基阴离子与二氧化碳的均相电子转移(ET)和产生中间体B的情况(图1路径b)不能被排除在外。
以1,1-二芳基乙烯类化合物为底物，当1,1-二芳基乙烯上的一个苯环被各种官能团取代时，如-OMe(1e，1j和1q)，-SMe(1f)，卤素(1g，1n，1r和1o)，-COOMe(1h和1l)，-CF3(1k)，-OCF3(1m)，都能很好的兼容在该反应体系中，并以较高的产率得到相应目标产物。此外，该反应对芳烃的电性不敏感，因为在芳基的对位带有给电子基(1e和1f)，电中性(1b，1c和1d)或吸电子基团(1h和1i)的底物，都可以顺利地转化为相应的所需产物，且能达到良好至极好的产率。另外，在间位取代(1j-1o)或邻位取代(1p-1r)的底物也可以很好地反应。此外，目前的方案可以进一步应用于带有萘(1s)和其他杂芳基取代的化合物，包括噻吩(1t)，呋喃(1u)和苯并呋喃(1v)。该反应中，重要一点是引入的烯烃(1x)和炔烃(1y)侧链并不参与反应，说明它们在该反应下耐受性良好，体现了双羧化反应的高化学选择性。
带有两个官能化芳基(1w，1z)的底物也可以高产率地生成所需产物(2w，2z)。值得注意的是，对抗癌药物Bexarotene(1aa)的后期修饰进行了测试，得到了所需的丁二酸类化产物，证明了该方案的有效性(2aa)。
除1,1-二芳基乙烯类化合物外，还测试了反应活性较低的单芳基取代烯烃(表2)。可以看出，各种α-烷基苯乙烯底物同样适合该双羧化反应。例如α-甲基苯乙烯(3b)和空间位阻更大的α-异丙基苯乙烯(3c)都能够反应。当使用(1-环丙基乙烯基)苯(3d)作为底物时，能主要得到丁二酸类化产物(4d)，同时产生痕量的开环产物，这可能是苄基的稳定性所致。此外，由于2-芳基丁二酸是液晶聚酯中的重要结构单元，因此在该反应中使用具有不同官能团(3e-3m)的单芳基取代烯烃，可合成一系列具有中等至良好收率的丁二酸类化合物。该反应同样也适用于β-取代的苯乙烯，例如1,2-二氢萘3n，得到所需的产物4n。
另外，将反应底物扩展到其他类型的烯烃，并进行了表3中的探索。当研究对象为丙烯酸酯(5a-5d)时，同样能在相同条件下获得丁二酸类化的主要产物。此外，联烯化合物4-(丁-2,3-二烯-2-基)-1,1'-联苯(表4)也能参与相关反应，尽管区域选择性较差，但收率良好。
对本发明涉及到的产物进行了核磁共振分析，表面得到的产物确实属于丁二酸类化合物。具体核磁数据如下：
2,2-二苯基丁二酸(2a)，2,2-diphenylsuccinic acid(2a)
Mp：173-175℃；
Rf(PE/EA1/4)：0.1；
1H NMR(400MHz,CD3OD)δ7.41–7.13(m,10H),3.48(s,2H).
13C NMR(101MHz,CD3OD)δ175.22,172.89,143.13,128.53,127.36,126.42,57.13,43.33.
1H NMR(400MHz,DMSO-d6)δ12.46(s,2H),7.41–7.23(m,8H),7.23–7.15(m,2H),3.39(s,2H).
13C NMR(101MHz,DMSO-d6)δ174.38,172.26,143.79,128.94,128.09,126.91,57.00,43.68.
ESI-MS(m/z)[M–H]-calcd for C16H13O4,270.09,found:268.91.
2-苯基-2-(4-甲基苯基)丁二酸(2b)，2-phenyl-2-(p-tolyl)succinic acid(2b)
Rf(PE/EA 2/3):0.09；
1H NMR(400MHz,DMSO-d6)δ12.41(s,2H),7.30–7.22(m,4H),7.22–7.18(m,1H),7.18–7.13(m,2H),7.07(d,J＝8.1Hz,2H),3.36(s,2H),2.25(s,3H).
13C NMR(101MHz,DMSO-d6)δ174.48,172.28,143.93,140.87,135.99,128.96,128.78,128.69,128.01,126.83,56.66,43.74,20.94.
ESI-MS(m/z)[M–H]-calcd for C17H15O4,284.10,found:282.91.
2-(4-(叔丁基)苯基)-2-苯基丁二酸(2c)，2-(4-(tert-butyl)phenyl)-2-phenylsuccinic acid(2c)
Rf(PE/EA 2/3):0.10；
1H NMR(400MHz,DMSO-d6)δ12.43(s,2H),7.38–7.23(m,6H),7.23–7.12(m,3H),3.44–3.29(m,3H),1.25(s,9H).
13C NMR(101MHz,DMSO-d6)δ174.49,172.30,149.05,143.89,140.70,128.90,128.55,128.06,126.81,124.88,56.64,43.66,34.53,31.56.
HRMS(ESI-):calculated m/z[M-H]-for[C20H21O4]-:325.1445,found:325.1441.
2-苯基-2-([1,1'-联苯]-4-基)丁二酸(2d)，2-([1,1'-biphenyl]-4-yl)-2-phenylsuccinic acid(2d)
Rf(PE/EA 2/3):0.09；
1H NMR(400MHz,DMSO-d6)δ12.49(s,2H),7.69–7.62(m,2H),7.61–7.54(m,2H),7.49–7.42(m,2H),7.41–7.26(m,7H),7.26–7.20(m,1H),3.44(s,2H).
13C NMR(101MHz,DMSO-d6)δ174.36,172.29,143.75,142.98,140.11,138.63,129.63,129.37,128.85,128.23,127.87,127.05,127.02,126.31,56.82,43.63.
HRMS(ESI+):calculated m/z[M+Na]+for[C22H18O4Na]+:369.1097,found:369.1092.
2-苯基-2-(4-甲氧基苯基)丁二酸(2e)，2-(4-methoxyphenyl)-2-phenylsuccinic acid(2e)
Rf(PE/EA1/1):0.10；
1H NMR(400MHz,CD3OD)δ7.36–7.30(m,2H),7.29–7.16(m,5H),6.86–6.74(m,2H),3.75(s,3H),3.45(d,J＝1.4Hz,2H).
13C NMR(101MHz,DMSO-d6)δ174.58,172.30,158.03,144.05,135.68,130.05,128.87,128.03,126.82,113.37,56.25,55.40,43.81.
13C NMR(101MHz,CD3OD)δ175.43,172.96,158.44,143.37,135.04,129.66,128.50,127.37,126.39,112.70,56.61,54.29,43.57.
HRMS(ESI-):calculated m/z[M-H]-for[C17H15O5]-:299.0925,found:299.0915.
2-苯-2-(4-甲硫基苯基)丁二酸(2f)，2-(4-(methylthio)phenyl)-2-phenylsuccinic acid(2f)
Rf(PE/EA 2/3):0.08；
1H NMR(400MHz,CD3OD)δ7.35–7.30(m,2H),7.29–7.17(m,5H),7.17–7.10(m,2H),3.57–3.38(m,2H),2.42(s,3H).
13C NMR(101MHz,CD3OD)δ175.16,172.88,143.06,139.82,137.20,129.16,128.41,127.48,126.52,125.29,56.76,43.28,14.18.
HRMS(ESI-):calculated m/z[M-H]-for[C17H15O4S]-:315.0697,found:315.0685.
2-苯基-2-(4-氟苯基)丁二酸(2g)，2-(4-fluorophenyl)-2-phenylsuccinicacid(2g)
Rf(PE/EA 2/3):0.13；
1H NMR(400MHz,DMSO-d6)δ12.52(s,2H),7.43–7.25(m,6H),7.26–7.20(m,1H),7.16–7.03(m,2H),3.44–3.33(m,3H).
13C NMR(101MHz,DMSO-d6)δ174.33,172.23,161.10(d,J＝243.5Hz),143.72,139.89,139.86,131.24(d,J＝8.0Hz),128.64,128.32,127.13,114.64(d,J＝21.1Hz),56.54,43.75.
19F NMR(376MHz,DMSO-d6)δ-116.55.
HRMS(ESI-):calculated m/z[M-H]-for[C16H12FO4]-:287.0725,found:287.0722.
2-苯基-2-(4-(甲氧羰基)苯基)丁二酸，2-(4-(methoxycarbonyl)phenyl)-2-phenylsuccinic acid(2h)
Rf(PE/EA 2/3):0.08；
1H NMR(400MHz,CD3OD)δ7.97–7.80(m,2H),7.50–7.41(m,2H),7.37–7.19(m,5H),3.86(s,3H),3.60(d,J＝16.7Hz,1H),3.44(d,J＝16.7Hz,1H).
13C NMR(101MHz,CD3OD)δ174.54,172.64,166.90,148.56,142.60,129.11,128.31,128.18,128.17,127.69,126.77,57.26,51.18,43.02.
HRMS(ESI+):calculated m/z[M+Na]+for[C18H16O6Na]+:351.0839,found:351.0831.
2-苯基-2-(4-羟基苯基)丁二酸(2i)，2-(4-hydroxyphenyl)-2-phenylsuccinicacid(2i)
Rf(PE/EA 1/2):0.05；
1H NMR(400MHz,CD3OD)δ7.35–7.30(m,2H),7.27–7.16(m,3H),7.16–7.07(m,2H),6.74–6.59(m,2H),3.50–3.36(m,2H).
13C NMR(101MHz,CD3OD)δ175.70,173.10,155.84,143.47,133.86,129.59,128.57,127.28,126.30,114.08,56.46,43.57.
HRMS(ESI-):calculated m/z[M-H]-for[C16H13O5]-:285.0768,found:285.0756.
2-苯基-2-(3-甲氧基苯基)丁二酸(2j)，2-(3-methoxyphenyl)-2-phenylsuccinic acid(2j)
1H NMR(400MHz,CD3OD)δ7.37–7.29(m,2H),7.29–7.14(m,4H),6.92(t,J＝2.2Hz,1H),6.86(dd,J＝7.8,1.8Hz,1H),6.79(dd,J＝8.2,2.5Hz,1H),3.71(s,3H),3.46(s,2H).
13C NMR(101MHz,CD3OD)δ175.14,172.88,159.18,144.58,142.96,128.52,128.31,127.33,126.44,120.70,114.99,111.61,57.09,54.18,43.37.
13C NMR(101MHz,DMSO-d6)δ174.98,172.26,157.52,140.68,132.08,130.80,129.23,128.55,127.83,127.01,119.93,112.65,55.97,55.87,39.09.
HRMS(ESI-):calculated m/z[M-H]-for[C17H15O5]-:299.0925,found:299.0912.
2-苯基-2-(3-(三氟甲基)苯基)丁二酸(2k)，2-phenyl-2-(3-(trifluoromethyl)phenyl)succinic acid(2k)
1H NMR(400MHz,CD3OD)δ7.81–7.74(m,1H),7.59–7.51(m,2H),7.43(t,J＝7.9Hz,1H),7.41–7.16(m,5H),3.70(d,J＝16.7Hz,1H),3.42(d,J＝16.8Hz,1H).
13C NMR(101MHz,CD3OD)δ174.51,172.58,144.37,142.52,132.77(q,J＝2.0Hz),129.29(q,J＝31.9Hz),127.97,127.91,127.89,126.99,126.01(q,J＝4.1Hz),124.30(d,J＝271.5Hz),123.08(q,J＝3.9Hz),56.96,43.03.
19F NMR(376MHz,CD3OD)δ-63.96.
HRMS(ESI-):calculated m/z[M-H]-for[C17H12F3O4]-:337.0693,found:337.0693.
2-苯基-2-(3-(甲氧羰基)苯基)丁二酸(2l)，2-(3-(methoxycarbonyl)phenyl)-2-phenylsuccinic acid(2l)
1H NMR(400MHz,CD3OD)δ8.06(t,J＝1.9Hz,1H),7.87(dt,J＝7.7,1.4Hz,1H),7.62–7.54(m,1H),7.40–7.18(m,6H),3.84(s,3H),3.61(d,J＝16.7Hz,1H),3.43(d,J＝16.7Hz,1H).
13C NMR(101MHz,CD3OD)δ174.72,172.68,167.08,143.78,142.77,133.83,129.97,129.29,128.19,127.75,127.50,127.46,126.80,57.03,51.25,43.11.
HRMS(ESI+):calculated m/z[M+Na]+for[C18H16O6Na]+:351.0839,found:351.0824.
2-苯基-2-(4-(三氟甲氧基)苯基)丁二酸(2m)，2-phenyl-2-(4-(trifluoromethoxy)phenyl)succinic acid(2m)
1H NMR(400MHz,CD3OD)δ7.36–7.11(m,8H),7.05(d,J＝7.8Hz,1H),3.56(d,J＝16.7Hz,1H),3.32(d,J＝16.7Hz,1H).
13C NMR(101MHz,CD3OD)δ174.50,172.57,148.34(q,J＝2.0Hz),145.71,142.50,128.63,128.00,127.79,127.62,126.91,122.27,120.49(q,J＝255.5Hz),118.80,56.87,43.07.
19F NMR(376MHz,CD3OD)δ-59.37.
HRMS(ESI-):calculated m/z[M-H]-for[C17H12F3O5]-:353.0642,found:353.0644.
2-苯基-2-(3-氟苯基)-丁二酸(2n)，2-(3-fluorophenyl)-2-phenylsuccinicacid(2n)
1H NMR(400MHz,CD3OD)δ7.37–7.31(m,2H),7.31–7.20(m,4H),7.18–7.11(m,1H),7.11–7.06(m,1H),6.98–6.89(m,1H),3.57(dd,J＝16.6,1.8Hz,1H),3.41(dd,J＝16.7,1.5Hz,1H).
13C NMR(101MHz,CD3OD)δ174.68,172.70,162.16(d,J＝243.1Hz),145.83(d,J＝7.3Hz),142.64,128.84(d,J＝8.7Hz),128.17,127.69,126.79,124.51(d,J＝2.9Hz),116.12(d,J＝23.5Hz),113.09(d,J＝21.3Hz),56.93(d,J＝1.7Hz),43.18.
19F NMR(376MHz,CD3OD)δ-115.60.
HRMS(ESI-):calculated m/z[M-H]-for[C16H12FO4]-:287.0725,found:287.0726.
2-苯基-2-(3-氯苯基)丁二酸(2o)，2-(3-chlorophenyl)-2-phenylsuccinicacid(2o)
1H NMR(400MHz,CD3OD)δ7.42–7.36(m,1H),7.36–7.15(m,8H),3.57(d,J＝16.6Hz,1H),3.39(d,J＝16.7Hz,1H).
13C NMR(101MHz,CD3OD)δ174.62,172.66,145.40,142.58,133.10,129.21,128.68,128.14,127.73,127.17,126.83,126.45,56.95,43.12.
HRMS(ESI-):calculated m/z[M-H]-for[C16H12ClO4]-:303.0430,found:303.0414.
2-苯基-2-(2-甲基苯基)丁二酸(2p)，2-phenyl-2-(o-tolyl)succinic acid(2p)
Rf(PE/EA 2/3):0.15
1H NMR(400MHz,CD3OD)δ7.51–7.44(m,1H),7.41–7.34(m,2H),7.28–7.13(m,5H),7.10–7.04(m,1H),3.61(d,J＝15.9Hz,1H),3.39(d,J＝15.8Hz,1H),1.85(s,3H).
13C NMR(101MHz,CD3OD)δ174.75,172.99,142.35,140.39,137.56,132.14,128.61,128.32,127.39,126.94,126.31,124.96,57.40,43.60,20.56.
HRMS(ESI-):calculated m/z[M-H]-for[C17H15O4]-:283.0976,found:283.0969.
2-苯基-2-(2-甲氧基苯基)丁二酸(2p)，2-(2-methoxyphenyl)-2-phenylsuccinic acid(2q)
Rf(PE/EA 2/3):0.10
1H NMR(400MHz,CD3OD)δ7.55–7.49(m,2H),7.35–7.19(m,4H),7.02(dd,J＝7.9,1.7Hz,1H),6.96(dd,J＝8.2,1.1Hz,1H),6.80(td,J＝7.6,1.2Hz,1H),3.71(s,3H),3.69(d,J＝16.8Hz,1H),3.53(d,J＝16.8Hz,1H).
13C NMR(101MHz,CD3OD)δ176.52,173.46,157.36,139.91,131.46,130.32,128.66,128.17,127.29,126.65,119.44,111.52,55.98,54.40,38.75.
HRMS(ESI-):calculated m/z[M-H]-for[C17H15O5]-:299.0925,found:299.0913.
2-苯基-2-(2-氟苯基)丁二酸(2r)，2-(2-fluorophenyl)-2-phenylsuccinicacid(2r)
Rf(PE/EA 2/3):0.15
1H NMR(400MHz,CD3OD)δ7.50–7.41(m,2H),7.38(td,J＝8.0,1.8Hz,1H),7.34–7.20(m,4H),7.06(td,J＝7.7,1.3Hz,1H),6.98(ddd,J＝12.2,8.2,1.3Hz,1H),3.65–3.47(m,2H).
13C NMR(101MHz,CD3OD)δ174.61,172.81,160.92(d,J＝247.1Hz),140.43,131.15(d,J＝3.7Hz),130.04(d,J＝11.0Hz),128.88(d,J＝9.0Hz),127.86,127.61,126.85,122.86(d,J＝3.3Hz),115.35(d,J＝23.3Hz),55.28,47.66,40.29(d,J＝3.0Hz).
19F NMR(376MHz,CD3OD)δ-109.48.
HRMS(ESI-):calculated m/z[M-H]-for[C16H12FO4]-:287.0725,found:287.0730.
2-苯基-2-(萘-2-基)丁二酸(2s)，2-(naphthalen-2-yl)-2-phenylsuccinicacid(2s)
Rf(PE/EA 2/3):0.08；
1H NMR(400MHz,DMSO-d6)δ12.56(s,2H),7.96(s,1H),7.92–7.82(m,2H),7.77(d,J＝8.8Hz,1H),7.55–7.46(m,2H),7.38–7.25(m,5H),7.25–7.19(m,1H),3.63–3.48(m,2H).
13C NMR(101MHz,DMSO-d6)δ174.34,172.31,143.64,141.09,132.80,132.04,129.11,128.56,128.16,127.85,127.65,127.41,127.01,126.95,126.59,57.17,43.69.
HRMS(ESI-):calculated m/z[M-H]-for[C20H15O4]-:319.0976,found:319.0965.
2-苯基-2-(噻吩-2-基)丁二酸(2t)，2-phenyl-2-(thiophen-2-yl)succinicacid(2t)
Rf(PE/EA 2/3):0.17；
1H NMR(400MHz,CD3OD)δ7.38–7.32(m,2H),7.31–7.19(m,4H),7.00(dd,J＝3.7,1.2Hz,1H),6.91(dd,J＝5.2,3.7Hz,1H),3.65(d,J＝16.8Hz,1H),3.45(d,J＝16.8Hz,1H).
13C NMR(101MHz,CD3OD)δ174.54,172.48,146.15,143.08,127.76,127.01,126.92,126.22,125.28,124.90,54.68,44.28.
HRMS(ESI-):calculated m/z[M-H]-for[C14H11O4S]-:275.0384,found:275.0385.
2-苯基-2-(呋喃-3-基)丁二酸(2u)，2-(furan-3-yl)-2-phenylsuccinic acid(2u)
Rf(PE/EA 2/3):0.11；
1H NMR(400MHz,DMSO-d6)δ12.42(s,2H),7.64(t,J＝1.1Hz,1H),7.53(t,J＝1.8Hz,1H),7.30(d,J＝4.2Hz,4H),7.26–7.20(m,1H),6.31(dd,J＝1.9,0.9Hz,1H),3.38(d,J＝16.7Hz,1H),3.21(d,J＝16.8Hz,1H).13C NMR(101MHz,DMSO-d6)δ174.18,172.10,142.85,142.76,141.21,128.56,127.72,127.46,127.32,111.74,51.35,43.10.
HRMS(ESI-):calculated m/z[M-H]-for[C14H11O5]-:259.0612,found:259.0607.
2-苯基-2-(苯并呋喃-2-基)丁二酸(2v)，2-(benzofuran-2-yl)-2-phenylsuccinic acid(2v)
Rf(PE/EA 2/3):0.15；
1H NMR(400MHz,CD3OD)δ7.59–7.51(m,1H),7.44–7.12(m,8H),7.06(s,1H),3.64(d,J＝16.9Hz,1H),3.51(d,J＝16.9Hz,1H).
13C NMR(101MHz,CD3OD)δ172.83,172.53,156.74,154.29,140.33,128.47,128.09,127.21,126.70,123.59,122.41,120.60,110.36,106.01,54.30,41.05.
HRMS(ESI+):calculated m/z[M+Na]+for[C18H14O5Na]+:333.0733,found:333.0729.
9-(羧甲基)-9H-噻吨-9-羧酸，9-(carboxymethyl)-9H-thioxanthene-9-carboxylic acid(2w)
Rf(PE/EA 2/3):0.16；
1H NMR(400MHz,CD3OD)δ7.47–7.40(m,2H),7.38–7.30(m,2H),7.28–7.13(m,4H),3.15(s,2H).
13C NMR(101MHz,CD3OD)δ174.56,172.27,134.60,131.33,128.71,126.99,125.98,125.86,125.80,55.94,39.24.
HRMS(ESI+):calculated m/z[M+Na]+for[C16H12O4SNa]+:323.0349,found:323.0351.
2-苯基-2-(4-(丁-2-炔-1-基氧基)苯基)丁二酸(2x)，2-(4-(but-2-yn-1-yloxy)phenyl)-2-phenylsuccinic acid(2x)
Rf(PE/EA2/3):0.18；
1H NMR(400MHz,CD3OD)δ7.36–7.30(m,2H),7.29–7.16(m,5H),6.90–6.78(m,2H),4.62(q,J＝2.3Hz,2H),3.45(s,2H),1.81(t,J＝2.3Hz,3H).
13C NMR(101MHz,CD3OD)δ175.13,172.65,156.30,142.97,135.23,129.28,128.13,127.05,126.07,113.27,82.42,73.51,56.19,55.33,43.16,1.42.
HRMS(ESI-):calculated m/z[M-H]-for[C20H17O5]-:337.1081,found:337.1074.
2-苯基-2-(4-(戊-4-烯-1-基氧基)苯基)丁二酸(2y)，2-(4-(pent-4-en-1-yloxy)phenyl)-2-phenylsuccinic acid(2y)
Rf(PE/EA2/3):0.23；
1H NMR(400MHz,CD3OD)δ7.37–7.30(m,2H),7.28–7.07(m,5H),6.87–6.71(m,2H),5.85(ddt,J＝17.0,10.2,6.7Hz,1H),5.07–4.96(m,2H),3.94(t,J＝6.3Hz,2H),3.51–3.37(m,2H),2.21(q,J＝7.0Hz,2H),1.88–1.75(m,2H).
13C NMR(101MHz,CD3OD)δ175.53,173.00,157.83,143.38,137.76,134.98,129.63,128.50,127.34,126.36,114.14,113.27,66.79,56.51,43.52,29.85,28.30.
HRMS(ESI-):calculated m/z[M-H]-for[C21H21O5]-:353.1394,found:353.1391.
2-苯基-2-(4-甲氧基苯基)-2-(4-氟苯基)丁二酸(2z)
3-2-(4-fluorophenyl)-2-(4-methoxyphenyl)succinic acid(2z)
6.96–6.87(m,2H),6.81–6.74(m,2H),3.71(s,3H),3.47(d,J＝16.5Hz,1H),3.32(d,J＝16.5Hz,1H).
13C NMR(101MHz,CD3OD)δ175.31,172.85,161.49(d,J＝244.7Hz),158.59,139.32(d,J＝3.4Hz),134.92,139.32(d,J＝3.4Hz),129.37,113.75(d,J＝21.4Hz),112.90,55.99,54.30,48.27,48.06,47.85,47.63,47.42,47.21,46.99,43.53.
19F NMR(376MHz,CD3OD)δ-118.43.
HRMS(ESI-):calculated m/z[M-H]-for[C17H14FO5]-:317.0831,found:337.0819.
2-(4-(甲氧基羰基)苯基)-2-(3,5,5,8,8-五甲基-5,6,7,8-四氢萘-2-基)丁二酸
2-(4-(methoxycarbonyl)phenyl)-2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)succinic acid
1H NMR(400MHz,CD3OD)δ7.95–7.81(m,2H),7.55–7.45(m,2H),7.38(s,1H),7.00(s,1H),3.87(s,3H),3.59(d,J＝16.0Hz,1H),3.38(d,J＝16.1Hz,1H),1.77(s,3H),1.69(s,3H),1.26(d,J＝3.7Hz,6H),1.24(d,J＝1.9Hz,6H).
13C NMR(101MHz,CD3OD)δ174.32,172.76,166.96,148.01,143.53,141.32,136.87,133.97,130.09,128.81,128.33,128.04,126.78,57.60,51.15,43.49,34.90,34.87,33.63,33.24,30.91,30.79,30.66,30.65,20.16.
HRMS(ESI+):calculated m/z[M+Na]+for[C27H32O6Na]+:475.2091,found:475.2106.
2-苯基丁二酸(4a)，2-phenylsuccinic acid(4a)
Mp:164–166℃；
Rf(PE/EA 2/3):0.13；
1H NMR(400MHz,CD3OD)δ7.45–7.15(m,5H),4.01(dd,J＝10.1,5.2Hz,1H),3.09(dd,J＝17.0,10.1Hz,1H),2.61(dd,J＝17.0,5.2Hz,1H).
13C NMR(101MHz,CD3OD)δ175.17,173.74,138.45,128.38,127.46,127.09,37.34.
ESI-MS(m/z)[M–H]-calcd for C10H9O4,194.06,found:192.89.
2-甲基-2-苯基丁二酸(4b)，2-methyl-2-phenylsuccinic acid(4b)
Mp:152–155℃；
Rf(PE/EA 2/3):0.25；
1H NMR(400MHz,CD3OD)δ7.55–7.50(m,2H),7.48–7.41(m,2H),7.38–7.31(m,1H),3.32(d,J＝16.6Hz,1H),2.93(d,J＝16.6Hz,1H),1.80(s,3H).
13C NMR(101MHz,CD3OD)δ177.37,173.27,143.35,128.13,126.60,125.41,47.79,42.90,22.61.
ESI-MS(m/z)[M–H]-calcd for C11H11O4,208.07,found:206.93.
2-异丙基-2-苯基丁二酸(4c)，2-isopropyl-2-phenylsuccinic acid(4c)
Mp:126–128℃；
Rf(PE/EA2/3):0.13；
1H NMR(400MHz,CD3OD)δ7.57–7.46(m,2H),7.46–7.36(m,2H),7.36–7.26(m,1H),3.32(d,J＝16.6Hz,1H),3.17(d,J＝16.6Hz,1H),2.65(hept,J＝6.8Hz,1H),1.00(d,J＝6.8Hz,3H),0.94(d,J＝6.8Hz,3H).13C NMR(101MHz,CD3OD)δ176.23,173.70,140.31,127.55,127.26,126.18,55.82,38.80,34.57,17.78,17.66.
HRMS(ESI-):calculated m/z[M-H]-for[C13H15O4]-:235.0976,found:235.0972.
2-环丙基-2-苯基丁二酸(4d)，2-cyclopropyl-2-phenylsuccinic acid(4d)
Mp:125–128℃；
Rf(PE/EA2/3):0.19；
1H NMR(400MHz,CD3OD)δ7.39–7.26(m,4H),7.26–7.20(m,1H),3.12(s,2H),1.74(tt,J＝8.6,5.6Hz,1H),0.57–0.45(m,1H),0.43–0.33(m,1H),0.11–0.00(m,2H).
13C NMR(101MHz,CD3OD)δ178.29,174.76,140.66,128.87,128.70,128.09,53.53,42.81,18.25,3.66,1.13.
HRMS(ESI-):calculated m/z[M-H]-for[C13H13O4]-:233.0819,found:233.0807.
2-([1,1'-联苯]-4-基)丁二酸(4e)，2-([1,1'-biphenyl]-4-yl)succinic acid(4e)
Rf(PE/EA 2/3):0.10；
1H NMR(400MHz,DMSO-d6)δ12.41(s,2H),7.72–7.56(m,4H),7.51–7.43(m,2H),7.42–7.29(m,3H),3.96(dd,J＝10.1,5.1Hz,1H),3.01(dd,J＝16.9,10.2Hz,1H),2.60(dd,J＝16.9,5.2Hz,1H).
13C NMR(101MHz,DMSO-d6)δ174.42,173.11,140.23,139.58,138.30,129.40,128.80,127.91,127.38,127.09,46.96,37.78.
ESI-MS(m/z)[M–H]-calcd for C16H13O4,270.09,found:268.99.
2-(4-甲基苯基)丁二酸(4f)，2-(p-tolyl)succinic acid(4f)
Mp:204–206℃；
1H NMR(400MHz,CD3OD)δ7.25–7.05(m,4H),3.96(dd,J＝10.3,5.2Hz,1H),3.07(dd,J＝17.0,10.2Hz,1H),2.58(dd,J＝17.0,5.2Hz,1H),2.30(s,3H).
13C NMR(101MHz,CD3OD)δ175.36,173.81,136.86,135.34,128.94,127.28,46.80,37.34,19.65.
ESI-MS(m/z)[M–H]-calcd for C11H11O4,207.07,found:207.03.
2-(4-(三氟甲基)苯基)丁二酸(4g)，2-(4-(trifluoromethyl)phenyl)succinicacid(4g)
Mp:192-194℃；
1H NMR(400MHz,CD3OD)δ7.69–7.58(m,2H),7.57–7.48(m,2H),4.13(dd,J＝9.7,5.5Hz,1H),3.13(dd,J＝17.0,9.8Hz,1H),2.68(dd,J＝17.0,5.6Hz,1H).
13C NMR(101MHz,CD3OD)δ174.35,173.42,142.98(q,J＝1.3Hz),129.22(q,J＝32.4Hz),125.55,125.18(q,J＝3.8Hz),124.20(q,J＝271.1Hz),47.10,36.95.
19F NMR(376MHz,CD3OD)δ-64.07.
HRMS(ESI-):calculated m/z[M-H]-for[C11H8F3O4]-:261.0380,found:261.0382.
2-(4-氰基苯基)丁二酸(4h)，2-(4-cyanophenyl)succinic acid(4h)
Mp:165–167℃；
1H NMR(400MHz,CD3OD)δ7.73–7.66(m,2H),7.55–7.44(m,2H),4.12(dd,J＝9.6,5.7Hz,1H),3.12(dd,J＝17.1,9.6Hz,1H),2.68(dd,J＝17.0,5.7Hz,1H).
13C NMR(101MHz,CD3OD)δ173.90,173.21,144.11,132.21,128.77,118.10,110.92,47.22,36.68.
HRMS(ESI-):calculated m/z[M-H]-for[C11H8NO4]-:218.0459,found:218.0458.
2-(4-氟苯基)丁二酸(4i)，2-(4-fluorophenyl)succinic acid(4i)
Mp:183–185℃；
1H NMR(400MHz,CD3OD)δ7.39–7.27(m,2H),7.11–6.98(m,2H),4.02(dd,J＝10.0,5.4Hz,1H),3.09(dd,J＝17.0,10.0Hz,1H),2.62(dd,J＝17.0,5.4Hz,1H).
13C NMR(101MHz,CD3OD)δ174.97,173.59,162.11(d,J＝244.4Hz),134.44,134.41,129.33(d,J＝8.2Hz),
114.98(d,J＝21.7Hz),46.41,37.25.
19F NMR(376MHz,CD3OD)δ-117.42.
HRMS(ESI-):calculated m/z[M-H]-for[C10H8FO4]-:211.0412,found:211.0412.
2-(3-氯苯基)丁二酸(4j)，2-(3-chlorophenyl)succinic acid(4j)
1H NMR(400MHz,CD3OD)δ7.42–7.16(m,4H),4.02(dd,J＝9.7,5.3Hz,1H),3.08(dd,J＝17.0,9.9Hz,1H),2.64(dd,J＝16.9,5.4Hz,1H).
13C NMR(101MHz,DMSO-d6)δ173.88,172.88,141.48,133.50,130.89,128.23,127.64,126.94,46.85,37.52.HRMS(ESI-):calculated m/z[M-H]-for[C10H8ClO4]-:227.0117,found:227.0109.
2-(2-甲基苯基)丁二酸(4k)，2-(o-tolyl)succinic acid(4k)
Rf(PE/EA2/3):0.30；
1H NMR(400MHz,CD3OD)δ7.32–7.03(m,4H),4.31(dd,J＝9.8,5.2Hz,1H),3.06(dd,J＝17.0,9.9Hz,1H),2.56(dd,J＝17.0,5.3Hz,1H),2.42(s,3H).
13C NMR(101MHz,CD3OD)δ175.42,173.92,136.92,136.02,130.31,126.94,126.20,126.03,42.81,36.69,18.39.
ESI-MS(m/z)[M–H]-calcd for C11H11O4,208.07,found:206.92.
2-(2-(烯丙氧基)苯基)丁二酸(4l)，2-(2-(allyloxy)phenyl)succinic acid(4l)
Rf(PE/EA2/3):0.31；
1H NMR(400MHz,CD3OD)δ7.25–7.15(m,2H),6.95(dd,J＝8.3,1.1Hz,1H),6.89(td,J＝7.5,1.1Hz,1H),6.15–5.99(m,1H),5.44(dq,J＝17.3,1.7Hz,1H),5.24(dq,J＝10.7,1.6Hz,1H),4.63–4.54(m,2H),4.36(dd,J＝9.4,5.3Hz,1H),3.04(dd,J＝16.8,9.4Hz,1H),2.55(dd,J＝16.8,5.3Hz,1H).
13C NMR(101MHz,CD3OD)δ175.48,174.27,155.82,133.24,128.67,128.24,127.35,120.48,115.77,111.99,68.52,42.10,36.10.
HRMS(ESI+):calculated m/z[M+Na]+for[C13H14O5Na]+:273.0733,found:273.0737.
2-(萘-1-基)丁二酸(4m)，2-(naphthalen-1-yl)succinic acid(4m)
Mp:171–173℃；
1H NMR(400MHz,CD3OD)δ8.20–8.13(m,1H),7.92–7.85(m,1H),7.83–7.77(m,1H),7.60–7.53(m,1H),7.52–7.47(m,1H),7.47–7.38(m,2H),4.88(dd,J＝10.2,4.7Hz,1H),3.23(dd,J＝17.0,10.2Hz,1H),2.71(dd,J＝17.1,4.7Hz,1H).
13C NMR(101MHz,CD3OD)δ175.42,173.96,134.75,134.22,131.14,128.60,127.70,126.10,125.43,125.06,124.62,122.78,42.91,37.10.
HRMS(ESI-):calculated m/z[M-H]-for[C14H11O4]-:243.0663,found:243.0660.
1,2,3,4-四氢化萘-1,2-二羧酸(4n)，1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid(4n)
Mp:137–139℃；
1H NMR(400MHz,CD3OD)δ7.40–7.25(m,1H),7.25–7.01(m,3H),4.07(d,J＝8.3Hz,1H),3.25–3.06(m,1H),2.93–2.78(m,2H),2.36–2.22(m,1H),1.95–1.77(m,1H).
13C NMR(101MHz,CD3OD)δ176.23,176.02,135.96,132.13,128.74,127.85,126.55,125.75,47.05,42.78,27.89,24.25.
HRMS(ESI-):calculated m/z[M-H]-for[C12H11O4]-:219.0663,found:219.0660.
2-甲基-2-([1,1'-联苯]-4-基)丁二酸(4o)，2-([1,1'-biphenyl]-4-yl)-2-methylsuccinic acid(4o)
Rf(PE/EA2/3):0.13；
1H NMR(400MHz,DMSO-d6)δ12.33(s,2H),7.64(t,J＝7.3Hz,4H),7.55–7.39(m,4H),7.36(t,J＝7.3Hz,1H),3.08(d,J＝16.5Hz,1H),2.83(d,J＝16.6Hz,1H),1.62(s,3H).
13C NMR(101MHz,DMSO-d6)δ176.32,172.72,143.20,140.13,139.03,129.39,127.89,127.11,127.06,126.79,47.70,43.26,23.80.
HRMS(ESI+):calculated m/z[M+Na]+for[C17H16O4Na]+:307.0941,found:307.0947.
2-甲基-2-(甲氧羰基)丁二酸(6a)，2-(methoxycarbonyl)-2-methylsuccinicacid(6a)
Mp:116–117℃；
1H NMR(400MHz,CD3OD)δ3.71(s,3H),2.97(d,J＝17.0Hz,1H),2.82(d,J＝17.0Hz,1H),1.52(s,3H).
13C NMR(101MHz,CD3OD)δ173.05,172.50,172.14,51.69,51.28,39.56,19.45.
HRMS(ESI-):calculated m/z[M-COOH]-for[C6H9O4]-:145.0506,found:145.0518.
2-甲基-2-((环己氧基)羰基)丁二酸(6b)，2-((cyclohexyloxy)carbonyl)-2-methylsuccinic acid(6b)
Rf(PE/EA 1/4):0.07；
Mp:90–92℃；
1H NMR(400MHz,CD3OD)δ4.80(td,J＝8.1,3.8Hz,1H),2.97(d,J＝17.0Hz,1H),2.82(d,J＝17.0Hz,1H),1.86–1.62(m,4H),1.59–1.24(m,9H).
13C NMR(101MHz,CD3OD)δ173.17,172.47,170.95,73.22,51.38,39.48,30.57,30.53,25.05,22.80,19.38.
HRMS(ESI-):calculated m/z[M-COOH]-for[C11H17O4]-:213.1132,found:213.1129.
2-甲基-2-(叔丁氧基羰基)丁二酸(6c)，2-(tert-butoxycarbonyl)-2-methylsuccinic acid(6c)
Rf(PE/EA 1/3):0.16；
1H NMR(400MHz,CD3OD)δ2.90(d,J＝16.9Hz,1H),2.77(d,J＝16.9Hz,1H),1.47(s,3H),1.44(s,9H).
13C NMR(101MHz,CD3OD)δ173.45,172.58,170.59,81.44,51.93,39.60,26.57,19.42.
HRMS(ESI-):calculated m/z[M-COOH]-for[C9H15O4]-:187.0976,found:187.0974.
2-甲基-2-(苯乙氧基羰基)丁二酸(6d)，2-methyl-2-(phenethoxycarbonyl)succinic acid(6d)
Mp:63–65℃；
1H NMR(400MHz,CD3OD)δ7.30–7.21(m,2H),7.21–7.08(m,3H),3.04–2.91(m,2H),2.61–2.49(m,2H),2.29–2.14(m,2H),1.47(s,9H).
13C NMR(101MHz,CD3OD)δ172.60,172.42,169.91,141.45,128.09,127.86,125.67,81.72,55.76,36.94,35.16,30.66,26.62.
HRMS(ESI-):calculated m/z[M-COOH]-for[C16H21O4]-:277.1445,found:277.1414.
虽然结合实施例对本发明的具体实施方式进行了详细地描述，但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内，本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。

Claims (8)

1.一种合成丁二酸类化合物的方法，其特征在于，所述方法具体为：
将底物、光催化剂和碱按1:0.005～0.5:1～20的摩尔比加入反应容器中，然后在CO2气氛下加入还原剂和溶剂，所加入的还原剂与底物的摩尔比为1～20:1；再在室温下搅拌反应2～48h，反应过程中用波长为400～550nm的可见光照射反应液；然后用2N的稀盐酸淬灭反应，再对反应后的混合物进行分离纯化，得丁二酸类化合物；
所述底物为1,1-二芳基乙烯类化合物(Ⅰ)、单芳基取代烯烃类化合物(Ⅱ)、丙烯酸酯类化合物(III)或4-(丁-2,3-二烯-2-基)-1,1'-联苯(IV)；
其中，R1为氢原子、烷基或卤原子；R2为氢原子、芳基、取代芳基、烷基、取代烷基、烃氧基、巯基、羟基、酯基或卤原子；R3为氢原子或烷基；R4为氢原子或烷基；R5和R6为烃基。
2.根据权利要求1所述的方法，其特征在于：所述光催化剂为4CzIPN、Ir[(ppy)2(dtbppy)]PF6、Ir[dF(CF3)ppy]2(dtbbpy)PF6、fac-Ir(ppy)3或Ru(bpz)3(PF6)2。
3.根据权利要求1所述的方法，其特征在于：所述碱为Cs2CO3、LiOtBu、NaOtBu、KOtBu、Na2CO3、K2CO3或CsF。
4.根据权利要求1所述的方法，其特征在于：所述还原剂为TMEDA、HEH、iPr2NEt或Et3N。
5.根据权利要求1所述的方法，其特征在于：所述光催化剂为4CzIPN，所述碱为Cs2CO3，底物、光催化剂和碱的摩尔比为1:0.02:4.5。
6.根据权利要求1所述的方法，其特征在于：所述还原剂为iPr2NEt，其与所述底物的摩尔比为1:1。
7.根据权利要求1所述的方法，其特征在于：所述溶剂为DMF、DMA、DMSO、NMP、MeCN、1,4-dioxane和MeOH中的至少一种。
8.根据权利要求1所述的方法，其特征在于：反应过程中用波长为450nm的可见光照射反应物，搅拌反应时间为24h。
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