CN111777477A - 一种丁二酸衍生物或3-芳基丙酸的合成方法 - Google Patents

一种丁二酸衍生物或3-芳基丙酸的合成方法 Download PDF

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CN111777477A
CN111777477A CN201911022392.0A CN201911022392A CN111777477A CN 111777477 A CN111777477 A CN 111777477A CN 201911022392 A CN201911022392 A CN 201911022392A CN 111777477 A CN111777477 A CN 111777477A
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余达刚
李静
黄河
叶剑衡
冉川昆
苗萌
王伟
陈瀚蛟
周文俊
于博
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Abstract

本发明公开了一种丁二酸衍生物或3‑芳基丙酸的合成方法，方法包括如下步骤：在干燥的反应管中加入碱，再在CO2的气氛下加入溶剂、硫酚和烯烃，在可见光照射下进行反应，原料反应完后，对反应所得混合物进行淬灭处理，之后进行分离纯化，即得丁二酸衍生物或3‑芳基丙酸产物；碱包括叔丁醇钠、叔丁醇钾、叔丁醇锂和碳酸钾；硫酚包括4‑叔丁基苯硫酚和2,4,6‑三异丙基苯硫酚；反应底物包括丙烯酸酯类化合物或芳基乙烯类化合物。本发明可以在可见光诱导、CO2参与下高效、高选择性地地合成丁二酸衍生物和3‑芳基丙酸；本发明方案的反应条件温和，反应底物选择性广，且放大至克级规模；本发明所用原料廉价易得，具有良好的工业应用前景。

Description

一种丁二酸衍生物或3-芳基丙酸的合成方法
技术领域
本发明属于有机合成技术领域，具体涉及一种丁二酸衍生物或3-芳基丙酸的合成方法。
背景技术
丁二酸的合成方法主要有六类：一是催化氧化石蜡；二是顺丁烯二酸酐或反丁烯二酸催化加氢；三是丙烯酸羰基合成法，将丙烯酸和一氧化碳在催化剂作用下，生成丁二酸；四是利用乙炔与一氧化碳及水在钴催化剂存在下，于酸性介质中反应产生丁二酸；五是电解法氧化顺丁烯二酸或顺酐；六是生物发酵法。上述六种方法中，除了生物发酵法和电解法之外，其余方法都需要使用贵金属催化剂和高温，条件苛刻；另外，丙烯酸羰基合成法尚未得到工业应用；电解法采用铅板为电极，容易造成重金属残留和污染，对电解设备要求也较高。
传统合成3-芳基丙酸的方法主要有四类：一是利用肉桂酸催化加氢的方法；二是通过铬酸盐氧化丙苯的方法；三是苄基丙二酸二乙酯合成3-芳基丙酸；四是芳基乙烯通过催化的方法与甲酸反应。上述方法中，催化加氢和芳基乙烯的羧化需要高压，对反应设备要求较高，并且需要昂贵的催化剂才能实现；铬酸盐氧化丙苯的方法存在氧化剂的浪费和过度氧化等问题；通过苄基丙二酸二乙酯合成3-芳基丙酸操作繁琐，原子经济性不高；而芳基乙烯的羧化反应往往伴随着α-羧基化的副产物产生。
与此同时，由于二氧化碳的大量排放，大气中CO2浓度持续增高，直接导致了全球气候日益变暖，海平面升高，生态环境恶化，自然灾害频发。因此，积极开展二氧化碳减排和合理利用的基础性研究，通过化学手段利用CO2制备重要有机化合物是一种非常重要的途径。如果能够实现其向具有重要价值的羧酸分子的高效转化，并实现其工业化大规模生产，不仅可以创造化工生产工业模式，降低生产成本，还将大大提高CO2资源的利用效率，为解决温室效应提供一种新的思路。目前化学家们已经实现了一些二氧化碳的转化并且获得的一系列具有高附加值化学品。然而，对二氧化碳的化学利用特别是实现其工业化的部分仅仅是冰山一角，其主要原因归结于二氧化碳的动力学稳定性和热力学惰性。因此，实现二氧化碳的化学利用，必须从二氧化碳的活化入手。随着对二氧化碳活化研究的深入，化学家们发展了一些不同的二氧化碳活化模式来促进二氧化碳的利用，如金属催化活化、路易斯酸碱协同活化、光电活化和生物酶催化活化等等，将这些活化模式应用于二氧化碳参与的反应中去，探索新的二氧化碳转化反应，推动二氧化碳的资源化利用进程，这具有重要的学术价值和实际意义。
由此，如何开发一种可以克服上述缺点的丁二酸衍生物和3-芳基丙酸的合成方法，并将CO2应用到羧酸分子的合成当中是本领域所亟需的。
发明内容
针对现有合成技术的缺点，本发明的目的在于提供一种丁二酸衍生物或3-芳基丙酸的合成方法，该方法具有产率高、反应条件温和、反应试剂毒性低、成本低等优点。本发明的合成方法包括如下步骤：
S1：将碱加入反应装置中，再在CO2的气氛下加入溶剂、反应底物、硫酚和添加剂，经脱气后得反应液；
S2：向装有反应液的反应装置中充入CO2气体，至反应装置内部压力为0.1Mpa；
S3：将反应液置于距可见光光源1cm处，在室温下搅拌反应24h，然后用淬灭剂淬灭反应，旋干溶剂得初产物；所述淬灭剂包括3体积份的乙酸乙酯和1.5体积份的盐酸或硫酸；
S4：通过快速柱层析纯化初产物，得丁二酸衍生物或3-芳基丙酸；
反应底物为丙烯酸酯类化合物或芳基乙烯类化合物；丙烯酸酯类化合物的结构式如式(III)所示，
Figure BDA0002247639970000021
R1和R2为氢或烷基，R3为烷基、烯基、芳香基或带取代基的芳香基，R4为如下基团中的一种，
Figure BDA0002247639970000022
芳基乙烯类化合物的结构式如式(IV)所示，
Figure BDA0002247639970000031
Ar为芳香基、带取代基的芳香基或杂芳基，R5为芳香基、带取代基的芳香基或烷基，R6为氢或烷基。
在上述技术方案的基础上，可以做如下进一步的改进。
进一步，碱的添加量为反应底物的2.5～3.0倍当量；所述硫酚的添加量为反应底物的2～3倍当量；所述添加剂的添加量为反应底物的1～3倍当量。
进一步，碱为叔丁醇钠、叔丁醇钾、叔丁醇锂或碳酸钾。
进一步，溶剂为DMF、DMA、NMP或DMSO。
进一步，硫酚为苯硫酚、4-甲基苯硫酚、4-叔丁基苯硫酚或2,4,6-三甲基苯硫酚。
进一步，添加剂为叔丁醇、正丁醇、异丙醇、三氟乙醇、六氟异丙醇、苯基甲醇、二苯基甲醇或三苯基甲醇。
进一步，S1中反应液脱气的具体方法为：将装有反应液的反应装置置于液氮下，待完全冰冻后，抽气5min；待完全解冻后再置于液氮下冷冻，完全冰冻后，抽气5min，完成脱气。
进一步，可见光光源为30W的蓝色LED灯。
进一步，S4中层析柱纯化所用洗脱液为石油醚、乙酸乙酯和冰醋酸的混合物，混合物中石油醚与乙酸乙酯的体积比为10:1，冰醋酸的质量分数为0.4～0.5％。
利用硫酚与丙烯酸酯体系合成丁二酸衍生物具有巨大挑战。首先，丙烯酸酯的α位和β位都有可能发生羧基化；其次，在可见光和碱性条件下，很容易发生迈克尔加成反应。另外，该体系也很难避免硫羧基化的副反应。为了避免上述问题，本发明的合成方法中利用CO2参与丙烯酸酯或芳基乙烯的羧化，具有较强的选择性，可在指定的位置形成羧基。
以丙烯酸酯丁酯(1a)作为起始原料对本发明的合成过程进行探究，合成按反应式(I)进行。在室温下一个大气压的CO2气氛里以不同的反应条件进行反应，部分反应条件如表1所示，表中标准反应条件为：1a(0.2mmol)，硫酚(0.4mmol)，碱(0.5mmol)，溶剂(2mL)，1atm CO2，30W蓝光照射，室温，24小时。N.D.为未检测到产物。
Figure BDA0002247639970000032
表1丙烯酸酯丁酯的反应条件及产率
Figure BDA0002247639970000041
从表中可以看出，当利用2倍当量的2,4,6-三异丙基苯硫酚，2.5倍当量的叔丁醇钠和2倍当量的叔丁醇时，可以得到目标产物丁二酸衍生物2a，且收率高达73％。之后，通过一系列的控制反应表明，硫酚、碱、可见光和二氧化碳对于这种转化都是必不可少的。如果不添加叔丁醇，产物2a的产率会明显降低。添加4-叔丁基苯硫酚时产率可达64％。
通过上述研究可以预见，在可见光驱动下利用芳基乙烯来合成3-芳基丙酸可能也是可行的。如表3所示，在现有的最优条件下，本发明成功地实现了以芳基乙烯3起始物，以较好的产率得到目标产物3-芳基丙酸4，3-芳基丙酸的合成反应式如式(II)所示，
Figure BDA0002247639970000042
3-芳基丙酸的结构及产率如表2所示。
表2 3-芳基丙酸的结构及产率
Figure BDA0002247639970000043
Figure BDA0002247639970000051
苯环上电中性取代基(3a-3c，3h，3l)以及给电子取代基(3d，3f，3i)对产率没有明显的影响。杂环取代的芳基乙烯(3g，3z)也能很好地兼容反应体系。值得一提的是，该反应体现出了很好的化学选择性，O-烯丙基取代的底物(3k)也能顺利地与CO2发生反应，且以较高的产率得到相应的产物。此外，在碱性条件下，苄醇取代的底物(3x)也能顺利的得到目标产物。α芳基取代和烷基取代的底物也显示出较好的反应性。最重要的是，抗糖尿病的GPR40活性药物(4ga)也能通过本发明中的方法进行高效的合成。结果进一步展示了本发明方法具有很好的应用前景。另外，三取代的芳基乙烯(3ka)也是可以兼容我们的反应体系，得到中等收率的目标产物。
在上述基础上，为了考察本发明方法的应用前景，进行放大反应以验证本发明是否能放大至克级规模。在标准反应条件下，以10mmol的芳基乙烯(3a)为起始底物，反应顺利进行，得到4a，产率78％。
根据上述内容可知，利用本发明中的合成方案，可制备得到式(2a)～(2ia)所示的丁二酸衍生物：
Figure BDA0002247639970000052
Figure BDA0002247639970000061
同样，利用本发明中的合成方案，可制备得到式(4a)～(4ka)所示的3-芳基丙酸化合物：
Figure BDA0002247639970000062
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衍生物和3-芳基丙酸；本发明方案的反应条件温和，反应底物选择性广，且放大至克级规模，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，所用原料廉价易得，具有良好的工业应用前景。
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：合成丁二酸衍生物
丁二酸衍生物的合成反应式如式(III)所示，
Figure BDA0002247639970000071
丁二酸衍生物的合成包括以下步骤：
S1：将加有磁子的干燥Schlenk管(10mL)转入手套箱中，加入叔丁醇钠(48mg，0.5mmol，2.5倍当量)；
S2：将Schlenk管从手套箱中取出并连接到连有CO2钢瓶的双排管上，在保证Schlenk管封闭的情况下，双排管上抽充CO2至少3次，排除支口中的N2，使其中充满CO2气体；
S3：在CO2气氛下加入NMP(2mL)、叔丁醇(38μL，0.4mmol，2倍当量)、2,4,6-三异丙基苯硫酚(95mg，0.4mmol，2倍当量)和反应底物(1)(0.2mmol)；
S4：将Schlenk管封好，置于液氮下，待完全冰冻后，打开Schlenk管保持抽气状态5min；随后封闭Schlenk管，待完全解冻后又置于液氮下脱气，如此操作2次；
S5：第二次解冻后，打开Schlenk管让其充入CO2气氛，至管内压力为1个大气压；
S6：将反应液置于距30W的蓝色LED光源1cm处，在室温(25℃)下搅拌反应24h；
S7：用3mL乙酸乙酯和1.5mL 2N盐酸淬灭反应，乙酸乙酯萃取6次后，直接浓缩旋干有机相，得初产物；
S8：初产物通过快速柱层析纯化得到纯的所需产物(2)，纯化所用洗脱液为石油醚、乙酸乙酯和冰醋酸的混合物，混合物中石油醚与乙酸乙酯的体积比为10:1，冰醋酸的质量分数为0.4～0.5％。
丁二酸衍生物的结构及产率如表3所示。
表3丁二酸衍生物的结构及产率
Figure BDA0002247639970000081
注：[b]d.r.值大约为1:1；[c]3mL NMP被使用；[d]d.r.值为3:1；[e]d.r.值为1:1；[f]丙烯酸酯的顺反比例为1:1。[g]d.r.值为5:1；[h]d.r.值大于19:1；[i]3倍硫酚和3.5倍碱被使用，反应48h。各化合物下方的百分数为产率，如“2a”为化合物的编号。
从表中可以看出，不同酯基取代的丙烯酸酯，如三级酯基取代底物1a-1e，二级酯基取代底物1f-1h和一级酯基取代底物1i-1j都能很好地兼容该体系中。另外，丙烯酸酯的α位除了甲基1a之外，其他一级取代基团1k-1o，二级取代基团1p-1r，三级取代基团1s，以及芳基取代1t-1w也都能以较好的收率得到目标产物。值得一提的是，烯丙基取代的丙烯酸酯1o表现出很好的化学选择性。此外，三取代的丙烯酸酯1x-1ba，甚至是四取代的丙烯酸酯1ca-1da也能得到相应的目标产物。综上所述，在本发明的体系下，一些活性分子修饰的丙烯酸酯都能很好地兼容。
丁二酸衍生物的结构表征如下：
4-(叔丁氧基)-3-甲基-4-氧代丁酸(2a)：浅黄色液体；1H NMR(400MHz,CDCl3)δ11.20(s,1H),2.86–2.68(m,2H),2.41(dd,J＝16.0,8.0Hz,1H),1.44(s,9H),1.20(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.21,174.34,80.66,37.47,36.46,27.81,16.87；MS(ESI-):187.09.
3-甲基-4-((1-甲基环戊基)氧基)-4氧代丁酸(2b)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.71(s,1H),2.83–2.66(m,2H),2.39(dd,J＝16.0,8.0Hz,1H),2.12–2.05(m,2H),1.70–1.58(m,6H),1.52(s,3H),1.18(d,J＝4.0Hz,3H)；13C NMR(101MHz,CDCl3)δ177.85,174.68,90.35,39.01,38.89,37.59,36.51,24.03,23.71,16.98；HRMS(ESI-):calcd forC11H17O4-[M-H]-213.1132,found 213.1134.
3-甲基-4-叔戊氧基氧代丁酸(2c)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.83–2.68(m,2H),2.40(dd,J＝8.0,4.0Hz,1H),1.77(q,J＝8.0,4.0Hz,2H),1.40(s,6H),1.20(d,J＝4.0Hz,3H),0.87(t,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ176.92,174.43,83.25,37.39,36.63,33.39,25.45,25.38,17.11,8.09；HRMS(ESI-):calcd for C10H17O4-[M-H]-201.1132,found 201.1136.
4-((3s,5s,7s)-1-金刚烷氧基-3-甲基-4-氧代丁酸(2d)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.83–2.65(m,2H),2.38(dd,J＝16.0,4.0Hz,1H),2.15(s,3H),2.09(s,6H),1.65(s,6H),1.19(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ177.78,174.44,80.78,41.14,37.81,36.75,36.15,30.79,17.06；HRMS(ESI-):calcd for C15H21O4-[M-H]-265.1445,found 265.1444.
3-甲基-4-((2-甲基-1-苯基丙烷-2-氧基)-4-氧代丁酸(2e)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.29–7.17(m,5H),3.05(q,J＝12.0Hz,2H),2.83–2.68(m,2H),2.38(dd,J＝16.0,4.0Hz,1H),1.43(d,J＝12.0Hz,6H),1.17(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.05,174.43,137.04,130.58,127.88,126.45,82.58,46.48,37.37,36.57,25.87,25.75,16.98；HRMS(ESI-):calcd for C15H19O4-[M-H]-263.1289,found 263.1290.
4-环己氧基-3-甲基-4-氧代丁酸(2f)：浅黄色液体；1H NMR(400MHz,CDCl3)δ4.79–4.73(m,1H),2.90–2.72(m,2H),2.43(dd,J＝16.0,8.0Hz,1H),1.79–1.68(m,4H),1.54–1.46(m,1H),1.43–1.27(m,5H),1.21(d,J＝4.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.04,174.51,72.81,37.38,35.81,31.31,25.31,23.48,16.94；HRMS(ESI-):calcd for C11H17O4-[M-H]-213.1132,found 213.1133.
4-异丙氧基-3-甲基-4-氧代丁酸(2g)：浅黄色液体；1H NMR(400MHz,CDCl3)δ5.05–4.98(m,1H),2.90–2.73(m,2H),2.43(dd,J＝16.0,4.0Hz,1H),1.23–1.20(m,9H)；13C NMR(101MHz,CDCl3)δ177.35,174.65,68.09,37.31,35.81,21.62,16.92；HRMS(ESI-):calcdfor C8H13O4-[M-H]-173.0819,found 173.0823.
3-甲基-4-(((3aS,4R,7S)-八氢-1H-4,7-甲基环戊二烯-2-氧基)-4-氧代丁酸(2h)：浅黄色液体；1H NMR(400MHz,CDCl3)δ4.57–4.56(m,1H),2.89–2.71(m,2H),2.42(dd,J＝16.0,4.0Hz,1H),2.05–2.61(m,2H),1.90–1.79(m,2H),1.77–1.72(m,2H),1.67–1.62(m,2H),1.42–1.36(m,1H),1.34–1.32(m,1H),1.26–1.24(m,2H),1.21(d,J＝4.0Hz,3H),1.00–0.86(m,2H)；13C NMR(101MHz,CDCl3)δ177.36,177.33,174.87,174.83,77.50,77.49,47.23,46.02,45.99,42.86,39.51,38.93,38.80,37.28,37.26,35.72,31.97,31.61,29.33,29.29,27.70,16.96,16.89；HRMS(ESI-):calcd for C15H21O4-[M-H]-265.1445,found 265.1445.
4-异丁氧基-3-甲基-4-氧代丁酸(2i)：浅黄色液体；1H NMR(400MHz,CDCl3)δ3.86(d,J＝8.0Hz,2H),2.90–2.74(m,2H),2.43(dd,J＝16.0,4.0Hz,1H),1.96–1.86(m,1H),1.23(d,J＝8.0Hz,3H),0.90(d,J＝8.0Hz,6H)；13C NMR(101MHz,CDCl3)δ178.05,175.10,70.85,37.29,35.60,27.63,18.94,18.92,16.96；HRMS(ESI-):calcd for C16H15O2S-[M-H]-187.0976,found 187.0982.
4-(2-乙基己氧基)-3-甲基-4-氧代丁酸(2j)：浅黄色液体；1H NMR(400MHz,CDCl3)δ4.05–3.96(m,2H),2.95–2.75(m,2H),2.45(dd,J＝16.0,4.0Hz,1H),1.60–1.54(m,1H),1.38–1.33(m,2H),1.28–1.27(m,5H),1.24(d,J＝8.0Hz,3H),0.89–0.86(m,7H)；13C NMR(101MHz,CDCl3)δ177.77,175.20,67.12,38.70,37.29,35.68,30.32,28.86,23.73,22.92,16.99,14.00,10.91；HRMS(ESI-):calcd for C13H23O4-[M-H]-243.1602,found 243.1598.
3-(叔丁氧羰基)戊酸(2k)：浅黄色液体；1H NMR(400MHz,CDCl3)δ8.13(s,1H),2.68–2.61(m,2H),2.41–2.34(m,1H),1.66–1.52(m,2H),1.43(s,9H),0.91(t,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.11,174.29,80.67,43.49,35.93,27.95,24.99,11.21；HRMS(ESI-):calcd for C10H17O4-[M-H]-201.1132,found 201.1135.
3-(叔丁氧羰基)庚酸(2l)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.70–2.64(m,2H),2.46–2.38(m,1H),1.66–1.57(m,1H),1.43(s,9H),1.31–1.25(m,5H),0.88(t,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.21,174.11,80.73,41.81,35.88,31.55,28.92,27.95,22.43,13.85；HRMS(ESI-):calcd for C12H21O4-[M-H]-229.1445,found 229.1445.
3-(叔丁氧羰基)-5-苯基戊酸(2m)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.29–7.25(m,2H),7.20–7.16(m,3H),2.78–2.60(m,4H),2.43(dd,J＝16.0,4.0Hz,1H),1.98–1.88(m,1H),1.82–1.75(m,1H),1.46(s,9H)；13C NMR(101MHz,CDCl3)δ177.66,174.19,141.37,128.41,128.34,126.00,80.95,41.94,36.53,33.79,33.19,28.00；HRMS(ESI-):calcd for C16H21O4-[M-H]-277.1445,found 277.1445.
3-苄基-4-(叔丁氧基)-4-氧代丁酸(2n)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.30–7.26(m,2H),7.23–7.16(m,3H),3.04–2.96(m,2H),2.78–2.61(m,2H),2.40(dd,J＝16.0,4.0Hz,1H),1.37(s,9H)；13C NMR(101MHz,CDCl3)δ178.07,173.19,138.23,129.09,128.44,126.60,81.05,43.61,37.69,35.08,27.84.MS(ESI-):263.11.All analyticaldata are consistent with those reported in the literature.2
3-(叔丁氧羰基)六-5-烯乌苏酸(2o)：浅黄色液体；1H NMR(400MHz,CDCl3)δ5.77–5.66(m,1H),5.09–5.05(m,2H),2.83–2.76(m,1H),2.66–2.60(m,1H),2.44–2.35(m,2H),2.30–2.23(m,1H),1.42(s,9H)；13C NMR(101MHz,CDCl3)δ177.72,173.53,134.54,117.66,80.99,41.60,35.98,35.42,27.97；HRMS(ESI-):calcd for C11H17O4-[M-H]-213.1132,found 213.1133.
3-(叔丁氧羰基)-4-甲基戊酸(2p)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.74–2.67(m,1H),2.62–2.57(m,1H),2.40(dd,J＝16.0,4.0Hz,1H),2.04–1.95(m,1H),1.44(s,9H),0.94(q,J＝12.0,4.0Hz,6H)；13C NMR(101MHz,CDCl3)δ177.50,173.47,80.80,48.04,32.67,30.02,28.00,20.03,19.43；HRMS(ESI-):calcd for C11H19O4-[M-H]-215.1289,found 215.1286.
4-(叔丁氧基)-3-环戊基-4-氧代丁酸(2q)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.78–2.67(m,1H),2.55–2.45(m,2H),1.99–1.89(m,1H),1.80–1.67(m,2H),1.64–1.58(m,2H)1.56–1.50(m,2H),1.43(s,9H),1.36–1.28(m,1H),1.22–1.17(m,1H)；13C NMR(101MHz,CDCl3)δ178.40,173.90,80.66,46.99,42.34,35.46,30.44,30.34,27.95,25.04,24.88；HRMS(ESI-):calcd for C13H21O4-[M-H]-241.1445,found241.1446.
4-(叔丁氧基)-4-氧-3-(四氢-2H-4-吡喃基)丁酸(2r)：浅黄色液体；1H NMR(400MHz,CDCl3)δ3.98(dd,J＝12.0,4.0Hz,2H),3.39–3.32(m,2H),2.72–2.56(m,2H),2.43(dd,J＝16.0,4.0Hz,1H),1.86–1.76(m,1H),1.54–1.50(m,2H),1.47–1.45(m,2H),1.43(s,9H)；13C NMR(101MHz,CDCl3)δ177.76,172.84,81.16,67.86,67.80,47.16,37.18,33.24,30.29,30.04,27.98；HRMS(ESI-):calcd for C13H21O5-[M-H]-257.1394,found 257.1396.
3-(叔丁氧羰基)-4,4-二甲基戊酸(2s)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.80–2.73(m,1H),2.51–2.44(m,2H),1.44(s,9H),0.97(s,9H)；13C NMR(101MHz,CDCl3)δ178.25,172.89,80.61,51.86,32.58,32.50,27.98,27.87；HRMS(ESI-):calcd forC12H21O4-[M-H]-229.1445,found 229.1440.
4-(叔丁氧基)-4-氧-3-苯基丁酸(2t)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.34–7.26(m,5H),3.96(q,J＝12.0,4.0Hz,1H),3.16(dd,J＝16.0,4.0Hz,1H),2.65(dd,J＝16.0,4.0Hz,1H),1.38(s,9H)；13C NMR(101MHz,CDCl3)δ176.69,172.02,138.11,128.73,127.60,127.40,81.31,48.08,37.66,27.81；MS(ESI-):249.09.
4-(叔丁氧基)-4-氧-3-对甲基苯基丁酸(2u)：白色固体；熔点122-124℃；1H NMR(400MHz,CDCl3)δ7.26–7.11(m,4H),3.91(dd,J＝8.0,4.0Hz,1H),3.16(dd,J＝16.0,12.0Hz,1H),2.63(dd,J＝16.0,4.0Hz,1H),2.33(s,3H),1.38(s,9H)；13C NMR(101MHz,CDCl3)δ177.68,172.04,137.09,135.00,129.45,127.45,81.22,47.55,37.71,27.84,21.07；HRMS(ESI-):calcd for C11H17O4-[M-H]-263.1289,found 263.1287.
4-(叔丁氧基)-4-氧-3-(4-甲氧基苯基)-4-氧代丁酸(2v)：白色固体，熔点119-120℃；1H NMR(400MHz,CDCl3)δ7.19(d,J＝12.0Hz,2H),6.85(d,J＝8.0Hz,2H),3.89(dd,J＝8.0,4.0Hz,1H),3.79(s,3H),3.14(dd,J＝16.0,8.0Hz,1H),2.63(dd,J＝16.0,4.0Hz,1H),1.38(s,9H)；13C NMR(101MHz,CDCl3)δ177.21,172.11,158.85,130.06,128.63,114.11,81.20,55.22,47.10,37.62,27.82；HRMS(ESI-):calcd for C15H19O5-[M-H]-279.1238,found 279.1237.
4-(叔丁氧基)-4-氧-3-(4-氟苯基)-4-氧代丁酸(2w)：浅黄色固体，熔点59-60℃；1H NMR(400MHz,CDCl3)δ7.22(dd,J＝8.0,4.0Hz,2H),6.99(t,J＝8.0Hz,2H),3.92(dd,J＝8.0,4.0Hz,1H),3.08(dd,J＝16.0,12.0Hz,1H),2.59(dd,J＝16.0,8.0Hz,1H),1.36(s,9H)；13C NMR(101MHz,CDCl3)δ177.22,172.11,162.04(d,J＝246.4Hz),133.93(d,J＝3.0Hz),129.20(d,J＝8.1Hz),115.58(d,J＝22.2Hz),81.46,47.45,38.02,27.76；19F NMR(376MHz,CDCl3)δ-115.17；HRMS(ESI-):calcd for C14H16FO4-[M-H]-267.1038,found267.1040.
4-(叔丁氧基)-2,3-二甲基-4-氧代丁酸(2x)：浅黄色液体，1H NMR(400MHz,CDCl3)δ2.74–2.67(m,2H),1.44(s,7.5H),1.43(s,1.5H),1.20–1.16(m,6H)；13C NMR(101MHz,CDCl3)δ180.08,173.95,81.07,42.98,42.32,27.92,14.77,14.10；HRMS(ESI-):calcd forC10H17O4-[M-H]-201.1132,found 201.1133.
4-(叔丁氧基)-2-乙基-3-甲基4-氧代丁酸(2y)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.69–2.50(m,2H),1.71–1.60(m,1H),1.55–1.47(m,1H),1.44(s,6H),1.42(s,3H),1.15(d,J＝8.0Hz,3H),0.95–0.91(m,3H)；13C NMR(101MHz,CDCl3)δ180.54,179.77,175.08,174.40,80.88,80.82,50.32,49.26,42.51,41.35,27.96,27.88,23.35,21.84,15.16,14.44,11.93,11.22；HRMS(ESI-):calcd for C11H19O4-[M-H]-215.1289,found215.1286.
2-(1-(叔丁氧基)-1-氧-2-丙酰基)戊酸(2z)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.67–2.56(m,2H),1.69–1.59(m,1H),1.44(s,7H),1.42(s,2H),1.15(d,J＝8.0Hz,3H),1.39–1.22(m,3H),0.93–0.88(m,3H)；13C NMR(101MHz,CDCl3)δ181.07,180.39,174.63,174.08,80.86,48.25,47.48,42.65,41.66,32.14,30.80,27.93,27.85,20.66,20.15,15.07,14.31,13.98,13.82；HRMS(ESI-):calcd for C12H21O4-[M-H]-229.1445,found229.1450.
4-(叔丁氧基)-3-甲基-4-氧-2-苯乙基丁酸(2aa)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.30–7.26(m,2H),7.20–7.17(m,3H),2.77–2.59(m,4H),2.07–1.99(m,1H),1.79–1.74(m,1H),1.44(s,1.5H),1.41(s,7.5H),1.17(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ180.72,180.03,174.28,173.78,141.29,141.14,128.63,128.55,128.41,128.38,126.12,126.02,82.11,81.00,47.76,47.11,42.60,41.64,33.67,33.28,31.59,30.40,27.88,27.54,14.89,14.09；HRMS(ESI-):calcd for C17H23O4-[M-H]-291.1602,found291.1606.
2-(叔丁氧羰基)环戊基甲酸(2ba)：浅黄色液体；1H NMR(400MHz,CDCl3)δ3.03–2.93(m,2H),2.03–1.82(m,5H),1.64–1.53(m,1H),1.40(s,9H)；13C NMR(101MHz,CDCl3)δ180.62,173.02,80.67,77.32,77.00,76.68,47.83,46.75,28.82,28.59,27.85,23.73；HRMS(ESI-):calcd for C11H17O4-[M-H]-213.1132,found 213.1137.
4-(叔丁氧基)-2,2,3-三甲基-4-氧代丁酸(2ca)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.80(q,J＝8.0Hz,1H),1.43(s,9H),1.22(d,J＝8.0Hz,6H),1.12(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ180.21,174.40,81.29,46.86,27.92,23.66,21.53,12.21；HRMS(ESI-):calcd for C11H19O4-[M-H]-215.1289,found 215.1285.
1-(1-(叔丁氧基)-1-氧-2-丙酰基环己基甲酸(2da)：浅黄色液体；1H NMR(400MHz,CDCl3)δ2.60–2.55(m,1H),2.10–2.01(m,2H),1.61–1.56(m,3H),1.45–1.41(m,10H),1.31–1.23(m,4H),1.15(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ180.84,174.03,81.15,48.95,48.32,31.50,31.44,27.91,25.61,23.12,23.10,12.38.；HRMS(ESI-):calcdfor C14H23O4-[M-H]-255.1602,found 255.1603.
3-甲基-4-氧-4-(((1R,2R,4R)-1,7,7-三甲基二环[2.2.1]-2-庚烷氧基)丁酸(2ea)：浅黄色液体；1H NMR(400MHz,CDCl3)δ4.64(dd,J＝8.0,4.0Hz,1H),2.91–2.73(m,2H),2.44(ddd,J＝20.0,8.0,4.0Hz,1H),1.82–1.66(m,4H),1.57–1.51(m,1H),1.24–1.21(m,3H),1.15–1.04(m,2H),0.96(d,J＝4.0Hz,3H),0.83(s,6H)；13C NMR(101MHz,CDCl3)δ177.76,174.47,174.43,81.46,81.45,48.70,48.67,46.90,46.88,44.98,38.68,38.67,37.26,35.89,35.81,33.72,27.00,26.99,20.07,19.85,19.83,16.98,16.92,11.34,11.32；HRMS(ESI-):calcd for C15H23O4-[M-H]-267.1602,found 267.1602.
4-(((1R,2S,5R)-2-异丙基-5-甲基环己基-3-氧基)-3-甲基-4-氧代丁酸(2fa)：浅黄色液体；1H NMR(400MHz,CDCl3)δ4.71–4.63(m,1H),2.91–2.74(m,2H),2.46–2.40(m,1H),2.01–1.84(m,2H),1.69–1.65(m,2H),1.49–1.36(m,2H),1.24–1.21(m,3H),1.09–0.93(m,3H),0.90–0.87(m,6H),0.73(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ177.60,177.53,174.78,174.73,74.59,74.46,46.98,46.96,40.65,40.64,37.43,37.33,35.94,35.89,34.24,31.35,31.34,26.15,26.06,23.38,23.21,22.00,21.99,20.79,20.69,17.08,17.01,16.15,16.00；HRMS(ESI-):calcd for C15H25O4-[M-H]-269.1758,found269.1754.
4-((1-异丙基-4-甲基环己基-3-烯-1-氧基)-3-甲基-4-氧代丁酸(2ga)：浅黄色液体；1H NMR(400MHz,CDCl3)δ6.35(s,1H),5.23(s,1H),2.87–2.63(m,3H),2.46–2.27(m,3H),2.15–2.11(m,1H),2.01–1.84(m,2H),1.70–1.57(m,4H),1.16(dd,J＝8.0,4.0Hz,3H),0.89–0.86(m,6H)；13C NMR(101MHz,CDCl3)δ177.70,177.67,174.95,174.93,133.58,133.42,117.57,117.50,86.54,86.48,37.92,37.04,32.40,29.83,29.80,27.75,27.58,27.40,27.26,23.08,23.05,17.62,17.45,17.22,17.20,17.07,16.87；HRMS(ESI-):calcdfor C15H23O4-[M-H]-267.1602,found 267.1598.
3-甲基-4-(2-(R)-4-甲基环己基-3-烯-2-丙酰基)-4-氧代丁酸(2ha)：浅黄色液体；1H NMR(400MHz,CDCl3)δ6.22(s,1H),5.36(s,1H),2.84–2.64(m,2H),2.36(dd,J＝16.0,8.0Hz,1H),2.02–1.92(m,4H),1.85–1.77(m,2H),1.63(s,3H),1.41(dd,J＝8.0,4.0Hz,6H),1.34–1.28(m,1H),1.18(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ177.63,174.69,133.95,133.89,120.31,120.25,85.30,42.91,42.87,37.96,36.98,36.96,30.85,26.30,26.27,23.85,23.82,23.29,23.22,23.14,23.06,22.98,17.12；HRMS(ESI-):calcd forC15H23O4-[M-H]-267.1602,found 267.1596.
4-胆固醇基-3-甲基-4-氧代丁酸(2ia)：白色固体，熔点169-171℃；1H NMR(400MHz,CDCl3)δ5.36(s,1H),4.65–4.57(m,1H),2.88–2.73(m,2H),2.44(dd,J＝16.0,8.0Hz,1H),2.31–2.28(m,2H),2.02–1.94(m,2H),1.86–1.78(m,3H),1.58–1.34(m,10H),1.23(d,J＝4.0Hz,3H),1.15–1.05(m,7H),1.04–0.95(m,4H),1.01(s,3H),0.91(d,J＝8.0Hz,3H),0.86(dd,J＝8.0,4.0Hz,6H),0.67(s,3H)；13C NMR(101MHz,CDCl3)δ177.69,177.68,174.54,174.51,139.53,139.50,122.68,122.66,74.31,56.66,56.12,49.98,39.71,39.49,37.90,37.36,36.93,36.55,36.16,35.78,31.88,31.83,28.21,27.99,27.59,27.58,24.27,23.82,22.81,22.55,21.02,19.30,18.70,16.99,11.84；HRMS(ESI-):calcd for C32H51O4-[M-H]-499.3793,found 499.3794.
实施例二：合成3-芳基丙酸
3-芳基丙酸的合成反应式如式(II)所示，
Figure BDA0002247639970000141
3-芳基丙酸的合成包括以下步骤：
S1：将装有磁子的干燥的Schlenk管(10mL)转入手套箱中，加入叔丁醇钠(48mg，0.5mmol，2.5倍当量)；
S2：将Schlenk管从手套箱中取出并连接到连有CO2钢瓶的双排管上，在保证Schlenk管封闭的情况下，双排管上抽充CO2至少3次，排除支口中的N2，使其中充满CO2气体；
S3：在CO2气氛下加入NMP(2mL)、叔丁醇(38μL，0.4mmol，2倍当量)、4-叔丁基苯硫酚(66.5mg，0.4mmol，2倍当量)和反应底物(3)(0.2mmol)；
S4：将Schlenk管封好，置于液氮下，待完全冰冻后，打开Schlenk管保持抽气状态5min，随后封闭Schlenk管，待完全解冻后又置于液氮下脱气，如此操作2次；
S5：第二次解冻后，打开Schlenk管让其充入CO2气氛，至管内压力为1个大气压；
S6：将反应液置于距30W的蓝色LED光源1cm处，在室温(25℃)下搅拌24h；
S7：用3mL乙酸乙酯和1.5mL 2N盐酸淬灭反应，然后直接浓缩旋干，得初产物；
S8：初产物通过快速柱层析纯化得到纯的所需产物(4)，纯化所用洗脱液为石油醚、乙酸乙酯和冰醋酸的混合物，混合物中石油醚与乙酸乙酯的体积比为10:1，冰醋酸的质量分数为0.4～0.5％。
3-芳基丙酸的结构及产率如表4所示。
表4 3-芳基丙酸的结构及产率
Figure BDA0002247639970000151
注：[b]克级规模。各化合物下方的百分数为产率，如“4a”为化合物的编号。
3-芳基丙酸的结构表征如下：
3-3-芳基丙酸(a)：白色固体,熔点46-47℃；1H NMR(400MHz,CDCl3)δ7.31–7.27(m,2H),7.23–7.19(m,3H),2.96(t,J＝8.0Hz,2H),2.68(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ179.37,140.16,128.59,128.28,126.40,35.65,30.59；MS(ESI-):149.09.
3-对甲基苯基丙酸(b)：白色固体，熔点118-120℃；1H NMR(400MHz,CDCl3)δ7.11(s,4H),2.93(t,J＝8.0Hz,2H),2.67(t,J＝8.0Hz,2H),2.33(s,3H)；13C NMR(101MHz,CDCl3)δ178.99,137.04,135.86,129.21,128.11,35.70,30.14,21.01；MS(ESI-):163.11.
3-(4-叔丁基苯基)丙酸(c)：白色固体,熔点112-113℃；1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.0Hz,2H),7.16(d,J＝8.0Hz,2H),2.94(t,J＝8.0Hz,2H),2.69(t,J＝8.0Hz,2H),1.32(s,9H)；13C NMR(101MHz,CDCl3)δ178.89,149.19,137.06,127.89,125.44,35.50,34.38,31.36,30.01；MS(ESI-):263.11.
3-(4-甲氧基苯基)丙酸(d)：白色固体,熔点101-103℃；1H NMR(400MHz,CDCl3)δ7.13(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,2H),3.19(s,3H),2.91(t,J＝8.0Hz,2H),2.65(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.56,158.12,132.21,129.21,113.95,55.25,35.80,29.74；MS(ESI-):179.01.
3-(4-氟苯基)丙酸(e)：白色固体,熔点88-89℃；1H NMR(400MHz,CDCl3)δ7.16(dd,J＝8.0,4.0Hz,2H),6.98(t,J＝8.0Hz,2H),2.93(t,J＝8.0Hz,2H),2.66(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.57,161.52(d,J＝245.4Hz),135.73(d,J＝3.0Hz),129.69(d,J＝8.1Hz),115.32(d,J＝22.2Hz),35.63,29.75；19F NMR(376MHz,CDCl3)δ-116.83；MS(ESI-):167.09.
3-(4-(二苯胺基)苯基)丙酸(f)：白色固体，熔点128-129℃；1H NMR(400MHz,CDCl3)δ7.25–7.21(m,4H),7.10–7.06(m,6H),7.03–6.97(m,4H),2.92(t,J＝8.0Hz,2H),2.68(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.42,147.84,146.14,134.53,129.15,129.04,124.42,123.94,122.52,35.53,29.96；HRMS(ESI-):calcd for C12H13O3 -[M-H]-316.1343,found 316.1345.
3-(4-(3-噻吩基)苯基)丙酸(g)：淡黄色固体，熔点207-209℃；1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.0Hz,2H),7.42(s,1H),7.37(d,J＝4.0Hz,2H),7.25(d,J＝8.0Hz,2H),2.99(t,J＝8.0Hz,2H),2.71(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.62,142.05,139.07,134.08,128.72,126.61,126.27,126.16,119.99,35.28,30.26.MS(ESI-):230.91.
3-(邻甲基苯基)丙酸(h)：白色固体，熔点105-106℃；1H NMR(400MHz,CDCl3)δ7.16–7.13(m,4H),2.96(t,J＝8.0Hz,2H),2.65(t,J＝8.0Hz,2H),2.33(s,3H)；13C NMR(101MHz,CDCl3)δ178.02,138.23,135.95,130.34,128.41,126.52,126.17,34.11,27.98,19.23；MS(ESI-):163.01.
3-(2-甲氧基苯基)丙酸(i)：浅黄色固体，熔点89-91℃；1H NMR(400MHz,CDCl3)δ7.23–7.17(m,2H),6.91–6.84(m,2H),3.83(s,3H),2.95(t,J＝8.0Hz,2H),2.67(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ179.24,157.44,129.92,128.45,127.69,120.42,110.17,55.13,33.87,25.87；MS(ESI-):179.01.
3-(2-氟苯基)丙酸(j)：黄色固体，熔点80-81℃；1H NMR(400MHz,CDCl3)δ7.24–7.18(m,2H),7.09–7.00(m,2H),2.99(t,J＝8.0Hz,2H),2.70(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.68,161.13(d,J＝246.4Hz),130.56(d,J＝5.0Hz),128.21(d,J＝8.0Hz),126.94(d,J＝15.2Hz),124.09(d,J＝4.0Hz),115.33(d,J＝22.2Hz),34.06(d,J＝1.0Hz),24.27(d,J＝3.0Hz)；19F NMR(376MHz,CDCl3)δ-118.47；MS(ESI-):167.09.
3-(2-(烯丙氧基)苯基)丙酸(k)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.21–7.17(m,2H),6.91–6.83(m,2H),6.11–6.02(m,1H),5.35(dd,J＝56.0,16.0Hz,2H),4.56(d,J＝4.0Hz,2H),2.99(t,J＝8.0Hz,2H),2.70(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ179.39,156.42,133.33,130.05,128.75,127.62,120.63,117.00,111.46,68.54,33.93,25.95；HRMS(ESI-):calcd for C12H13O3 -[M-H]-205.0870,found205.0865.
3-(间甲基苯基)丙酸(l)：浅黄色固体，熔点44-45℃；1H NMR(400MHz,CDCl3)δ7.20(t,J＝8.0Hz,1H),7.05–7.01(m,3H),2.94(t,J＝8.0Hz,2H),2.69(t,J＝8.0Hz,2H),2.34(s,3H)；13C NMR(101MHz,CDCl3)δ179.13,140.07,138.13,129.04,128.44,127.09,125.21,35.62,30.50,21.36；MS(ESI-):163.09.
3-(3-甲氧基苯基)丙酸(m)：浅黄色固体，熔点46-48℃；1H NMR(400MHz,CDCl3)δ7.23–7.19(m,1H),6.81–6.75(m,3H),3.80(s,3H),2.94(t,J＝8.0Hz,2H),2.68(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.45,159.72,141.75,129.54,120.57,114.06,111.68,55.15,35.40,30.62；MS(ESI-):179.07.
3-(3-氟苯基)丙酸(n)：浅黄色固体，熔点:45-46℃；1H NMR(400MHz,CDCl3)δ7.24–7.20(m,1H),6.97–6.87(m,3H),2.94(t,J＝8.0Hz,2H),2.67(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.66,162.91(d,J＝246.4Hz),142.61(d,J＝7.1Hz),130.0(d,J＝8.1Hz),123.89(d,J＝2.0Hz),115.20(d,J＝21.2Hz),113.30(d,J＝21.2Hz),35.21,30.22(d,J＝2.0Hz)；19F NMR(376MHz,CDCl3)δ-113.33；MS(ESI-):167.09.All analytical dataare consistent with those reported in the literature.7
3-(3-苯氧基苯基)丙酸(o)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.33(t,J＝8.0Hz,2H),7.25(t,J＝8.0Hz,1H),7.10(t,J＝8.0Hz,1H),7.00(d,J＝8.0Hz,2H),6.95(d,J＝8.0Hz,1H),6.87–6.84(m,2H),2.93(t,J＝8.0Hz,2H),2.66(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.51,157.40,157.08,142.20,129.79,129.72,123.24,123.08,118.90,118.69,116.73,35.42,30.46；HRMS(ESI-):calcd for C11H17O4 -[M-H]-241.0870,found 241.0868.
3-(4-氟-3-甲基苯基)丙酸(p)：白色固体，熔点65-66℃；1H NMR(400MHz,CDCl3)δ7.02–6.96(m,2H),6.93–6.89(m,1H),2.89(t,J＝8.0Hz,2H),2.65(t,J＝8.0Hz,2H),2.24(d,J＝4.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.34,160.04(d,J＝244.4Hz),135.44(d,J＝4.0Hz),131.25(d,J＝5.1Hz),126.87(d,J＝8.1Hz),124.74(d,J＝17.2Hz),114.91(d,J＝22.2Hz),35.64,29.76,14.52(d,J＝4.0Hz)；19F NMR(376MHz,CDCl3)δ-121.25；HRMS(ESI-):calcd for C11H17O4 -[M-H]-181.0670,found 181.0673.
3-(3-氟-4-甲基苯基)丙酸(q)：白色固体，熔点91-92℃；1H NMR(400MHz,CDCl3)δ7.09(t,J＝8.0Hz,1H),6.88–6.85(m,2H),2.92(t,J＝8.0Hz,2H),2.66(t,J＝8.0Hz,2H),2.23(d,J＝4.0Hz,3H)；13C NMR(101MHz,CDCl3)δ177.67,161.25(d,J＝245.4Hz),139,72(d,J＝8.1Hz),131.43(d,J＝6.1Hz),123.55(d,J＝3.0Hz),122.65(d,J＝17.2Hz),114.79(d,J＝22.2Hz),35.19,29.94(d,J＝2.0Hz),14.15(d,J＝3.0Hz)；19F NMR(376MHz,CDCl3)δ-117.66；HRMS(ESI-):calcd for C11H17O4 -[M-H]-181.0670,found 181.0674.
3-(4-氟-3-苯氧基苯基)丙酸(r)：浅黄色固体，熔点60-61℃；1H NMR(400MHz,CDCl3)δ7.34–7.30(m,2H),7.12–7.07(m,2H),6.98–6.89(m,4H),2.88(t,J＝8.0Hz,2H),2.63(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.30,157.26,152.94(d,J＝247.4Hz),143.48(d,J＝12.1Hz),136.88(d,J＝4.0Hz),129.69,124.36(d,J＝6.1Hz),123.12,121.62(d,J＝2.0Hz),117.25,116.98(d,J＝19.2Hz),35.40,29.8；19F NMR(376MHz,CDCl3)δ-134.15；HRMS(ESI-):calcd for C11H17O4 -[M-H]-259.0776,found 259.0776.
3-(2,4-二甲基苯基)丙酸(s)：白色固体，熔点108-109℃；1H NMR(400MHz,CDCl3)δ7.05–7.04(m,1H),6.98–6.95(m,2H),2.92(t,J＝8.0Hz,2H),2.63(t,J＝8.0Hz,2H),2.29(s,6H)；13C NMR(101MHz,CDCl3)δ178.57,136.00,135.75,135.16,131.15,128.38,126.78,34.38,27.61,20.89,19.15；MS(ESI-):177.09.
3-(4-氟-2-甲基苯基)丙酸(t)：白色固体，熔点112-113℃；1H NMR(400MHz,CDCl3)δ7.11–7.08(m,1H),6.88–6.80(m,2H),2.92(t,J＝8.0Hz,2H),2.62(t,J＝8.0Hz,2H),2.31(s,3H)；13C NMR(101MHz,CDCl3)δ178.37,161.38(d,J＝244.4Hz),138.14(d,J＝8.1Hz),133.81(d,J＝3.0Hz),129.80(d,J＝8.1Hz),116.93(d,J＝21.2Hz),112.69(d,J＝21.2Hz),34.30,27.25,19.35(d,J＝2.0Hz)；19F NMR(376MHz,CDCl3)δ-117.31；MS(ESI-):181.07.
3-(2-氟-4-甲氧基苯基)丙酸(u)：浅黄色固体，熔点87-88℃；1H NMR(400MHz,CDCl3)δ7.12–7.08(m,1H),6.63–6.58(m,2H),3.77(s,3H),2.91(t,J＝8.0Hz,2H),2.64(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.81,161.52(d,J＝246.4Hz),159.52(d,J＝11.1Hz),130.77(d,J＝7.1Hz),118.77(d,J＝6.1Hz),109.66(d,J＝3.0Hz),101.65(d,J＝25.2Hz),55.5,34.46(d,J＝1.0Hz),23.73(d,J＝2.0Hz)；19F NMR(376MHz,CDCl3)δ-116.33；MS(ESI-):197.06.
3-(4-甲氧基-2-三氟甲基苯基)丙酸(v)：浅绿色固体，熔点84-85℃；1H NMR(400MHz,CDCl3)δ7.24(d,J＝7.0Hz,1H),7.13(d,J＝2.0Hz,1H),6.98(dd,J＝8.0Hz,4.0Hz,1H),3.80(s,3H),3.04(t,J＝8.0Hz,2H),2.61(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.71,157.84,132.18,130.64(d,J＝1.0Hz),129.40(q,J＝30.3Hz),124.22(q,J＝275.7Hz),117.23(d,J＝1.0Hz),111.83(q,J＝6.1Hz),55.43,36.16,26.89(d,J＝1.0Hz)；19F NMR(376MHz,CDCl3)δ-60.12；HRMS(ESI-):calcd for C11H17O4 -[M-H]-247.0588,found 247.0584.
3-(2,4,5-三甲基苯基)丙酸(w)：白色固体，熔点97-98℃；1H NMR(400MHz,CDCl3)δ6.93(d,J＝4.0Hz,2H),2.91(t,J＝8.0Hz,2H),2.63(t,J＝8.0Hz,2H),2.27(s,3H),2.22(s,6H)；13C NMR(101MHz,CDCl3)δ179.27,135.49,134.53,134.07,133.04,131.73,129.89,34.65,27.60,19.19,19.13,18.57；HRMS(ESI-):calcd for C11H17O4 -[M-H]-191.1078,found 191.1077.
3-(4-(羟甲基)苯基)丙酸(x)：白色固体，熔点146-147℃；1H NMR(400MHz,DMSO-d6)δ12.08(s,1H),7.20–7.13(m,4H),5.07(t,J＝4.0Hz,1H),4.42(d,J＝4.0Hz,2H),2.77(t,J＝8.0Hz,2H),2.48–2.46(m,2H)；13C NMR(101MHz,DMSO-d6)δ173.74,140.15,139.18,127.90,126.52,62.74,35.35,30.05；HRMS(ESI-):calcd for C11H17O4 -[M-H]-179.0714,found 179.0715.
3-(2-萘基)丙酸(y)：黄色固体，熔点134-136℃；1H NMR(400MHz,CDCl3)δ7.83–7.78(m,3H),7.66(s,1H),7.49–7.43(m,2H),7.35(d,J＝8.0Hz,1H),3.14(t,J＝8.0Hz,2H),2.79(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ178.85,137.60,133.54,132.16,128.18,127.60,127.50,126.85,126.44,126.05,125.43,35.47,30.72；MS(ESI-):199.08.
3-(1-(叔丁氧羰基)-1H--5-吲哚基)丙酸(z)：黄色固体，熔点102-104℃；1H NMR(400MHz,CDCl3)δ8.04(d,J＝8.0Hz,1H),7.57(d,J＝4.0Hz,1H),7.39(s,1H),7.16(d,J＝8.0,1H),6.51(d,J＝4.0Hz,1H),3.05(t,J＝8.0Hz,2H),2.72(t,J＝8.0Hz,2H),1.66(s,9H)；13C NMR(101MHz,CDCl3)δ178.61,149.75,134.51,130.84,126.17,124.65,120.25,115.13,107.08,83.61,36.10,30.54,28.18；MS(ESI-):288.10.
3,3-二苯基丙酸(aa)：浅黄色固体，熔点153-154℃；1H NMR(400MHz,CDCl3)δ7.29–7.16(m,10H),4.51(t,J＝8.0Hz,1H),3.07(d,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.39,143.21,128.60,127.59,126.61,46.59,40.35；MS(ESI-):225.09.
3-(4-甲氧基苯基)-3-苯基丙酸(ba)：浅黄色固体，熔点119-121℃；1H NMR(400MHz,CDCl3)δ7.29–7.25(m,2H),7.21–7.18(m,3H),7.14(d,J＝8.0Hz,2H),6.81(d,J＝8.0Hz,2H),4.47(t,J＝8.0Hz,1H),3.76(s,3H),3.05(t,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.66,158.13,143.72,135.48,128.56,127.50,126.45,113.94,55.17,45.90,40.85；MS(ESI-):255.10.
3-(4-氟苯基)-3-苯基丙酸(ca)：浅黄色固体，熔点111-112℃；1H NMR(400MHz,CDCl3)δ7.30–7.24(m,2H),7.21–7.16(m,5H),6.98–6.93(m,2H),4.50(t,J＝8.0Hz,1H),3.05(dd,J＝8.0,2.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.52,161.53(d,J＝246.4Hz),142.99,138.92,129.08(d,J＝8.1Hz),128.69,127.46,126.76,115.42(d,J＝22.2Hz),45.86,40.49；19F NMR(376MHz,CDCl3)δ-116.29；MS(ESI-):243.09.
3-(4-氟苯基)-3-(4-甲氧基苯基)丙酸(da)：浅黄色固体，熔点85-87℃；1H NMR(400MHz,CDCl3)δ7.15–7.12(m,2H),7.09(d,J＝8.0Hz,2H),6.93(t,J＝8.0Hz,2H),6.80(d,J＝8.0Hz,2H),4.42(t,J＝8.0Hz,1H),3.75(s,3H),2.96(d,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.29,161.43(d,J＝245.4Hz),158.24,139.45(d,J＝3.0Hz),135.27,128.98(d,J＝8.1Hz),128.45,115.33(d,J＝21.2Hz),114.02,55.19,45.22,41.01；19F NMR(376MHz,CDCl3)δ-116.52；HRMS(ESI-):calcd for C11H17O4 -[M-H]-273.0932,found273.0933.
3,3-二(4-氟苯基)丙酸(ea)：浅黄色固体，熔点109-110℃；1H NMR(400MHz,CDCl3)δ7.18–7.14(m,4H),6.99–6.95(m,4H),4.49(t,J＝8.0Hz,1H),3.03(d,J＝8.0Hz,2H)；13CNMR(101MHz,CDCl3)δ176.71,161.59(d,J＝246.4Hz),138.72(d,J＝4.0Hz),128.99(d,J＝8.1Hz),115.53(d,J＝21.2Hz),45.18,40.56；19F NMR(376MHz,CDCl3)δ-116.02；MS(ESI-):261.08.
3,3-二(4-甲氧基苯基)丙酸(fa)：浅黄色固体，熔点136-138℃；1H NMR(400MHz,CDCl3)δ7.12(d,J＝8.0Hz,4H),6.80(d,J＝8.0Hz,4H),4.42(t,J＝8.0Hz,1H),3.75(s,6H),2.99(d,J＝8.0Hz,2H)；13C NMR(101MHz,CDCl3)δ177.63,158.07,135.85,128.45,113.91,55.17,45.09,41.01；MS(ESI-):285.03.
3-苯基-3-(4-丙氧基苯基)丙酸(ga)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.27–7.16(m,5H),7.11(d,J＝8.0Hz,2H),6.79(d,J＝8.0Hz,2H),4.44(t,J＝8.0Hz,1H),3.85(t,J＝8.0Hz,2H),3.01(d,J＝8.0Hz,2H),1.81–1.72(s,2H),1.00(d,J＝8.0Hz,3H)；13CNMR(101MHz,CDCl3)δ177.41,157.71,143.77,135.26,128.53,127.51,126.43,114.49,69.40,45.92,40.83,22.57,10.52.HRMS(ESI-):calcd for C18H19O3 -[M-H]-283.1340,found 283.1341.
3-苯基丁酸(ha)：浅黄色液体；1H NMR(400MHz,CDCl3)δ7.31–7.27(m,2H),7.22–7.18(m,3H),3.30–3.21(m,1H),2.68–2.52(m,2H),1.31(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ178.41,145.52,128.52,126.68,126.44,42.73,36.19,21.82.MS(ESI-):163.10.
3,4-二苯基丁酸(ia)：白色固体，熔点96-97℃；1H NMR(400MHz,CDCl3)δ7.24–7.11(m,8H),7.02(d,J＝8.0Hz,2H),3.41–3.34(m,1H),2.89(dd,J＝8.0,4.0Hz,2H),2.71–2.59(m,2H)；13C NMR(101MHz,CDCl3)δ178.35,143.10,139.27,129.18,128.39,128.19,127.43,126.63,126.19,43.55,42.95,39.75；MS(ESI-):239.01.
2-(1,2,3,4-四氢-1-萘基)乙酸(ja)：浅黄色液体；1H NMR(400MHz,CDCl3)δ8.74(s,1H),7.22–7.08(m,4H),3.40–3.34(m,1H),2.84–2.76(m,3H),2.63–2.56(m,1H),2.00–1.93(m,1H),1.90–1.73(m,3H)；13C NMR(101MHz,CDCl3)δ179.08,138.98,137.13,129.28,128.19,126.07,125.87,41.90,34.36,29.47,28.03,19.46；MS(ESI-):188.96.
2-甲基-3,3-二苯基丙酸(ka)：白色固体，熔点163-164℃；1H NMR(400MHz,CDCl3)δ7.31-7.13(m,10H),4.06(d,J＝12.0Hz,1H),3.34(m,1H),1.14(d,J＝8.0Hz,3H)；13C NMR(101MHz,CDCl3)δ180.17,142.86,142.03,128.68,128.52,128.14,127.52,126.64,126.54,54.68,44.06,17.13.HRMS(ESI-):calcd for C16H15O2 -[M-H]-239.1078,found239.1086.
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 (10)

1.一种丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于，包括如下步骤：
S1：将碱加入反应装置中，再在CO2的气氛下加入溶剂、反应底物、硫酚和添加剂，经脱气后得反应液；
S2：向装有反应液的反应装置中充入CO2气体，至反应装置内部压力为0.1Mpa；
S3：将反应液置于距可见光光源1cm处，在室温下搅拌反应24h，然后用淬灭剂淬灭反应，旋干溶剂得初产物；所述淬灭剂包括3体积份的乙酸乙酯和1.5体积份的盐酸或硫酸；
S4：通过快速柱层析纯化初产物，得丁二酸衍生物或3-芳基丙酸；
所述反应底物为丙烯酸酯类化合物或芳基乙烯类化合物。
2.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述丙烯酸酯类化合物的结构式如式(III)所示，
Figure FDA0002247639960000011
R1和R2为氢或烷基，R3为烷基、烯基、芳香基或带取代基的芳香基，R4为如下基团中的一种，
Figure FDA0002247639960000012
所述芳基乙烯类化合物的结构式如式(IV)所示，
Figure FDA0002247639960000021
Ar为芳香基、带取代基的芳香基或杂芳基，R5为芳香基、带取代基的芳香基或烷基，R6为氢或烷基。
3.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述碱的添加量为反应底物的2.5～3.0倍当量；所述硫酚的添加量为反应底物的2～3倍当量；所述添加剂的添加量为反应底物的1～3倍当量。
4.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述碱为叔丁醇钠、叔丁醇钾、叔丁醇锂或碳酸钾。
5.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述溶剂为DMF、DMA、NMP或DMSO。
6.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述硫酚为苯硫酚、4-甲基苯硫酚、4-叔丁基苯硫酚或2,4,6-三甲基苯硫酚。
7.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述添加剂为叔丁醇、正丁醇、异丙醇、三氟乙醇、六氟异丙醇、苯基甲醇、二苯基甲醇或三苯基甲醇。
8.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于，S1中反应液脱气的具体方法为：将装有反应液的反应装置置于液氮下，待完全冰冻后，抽气5min；待完全解冻后再置于液氮下冷冻，完全冰冻后，抽气5min，完成脱气。
9.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于：所述可见光光源为30W的蓝色LED灯。
10.根据权利要求1所述的丁二酸衍生物或3-芳基丙酸的合成方法，其特征在于，S4中层析柱纯化所用洗脱液为石油醚、乙酸乙酯和冰醋酸的混合物，混合物中石油醚与乙酸乙酯的体积比为10:1，冰醋酸的质量分数为0.4～0.5％。
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