CN107955032B - 中间体化合物及其制备方法 - Google Patents
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Abstract
本发明涉及一种中间体化合物及其制备方法，属于手性天然产物的合成领域。该中间体化合物化学式为
Description
本申请为申请号201610147382X，申请日为2016年3月16日，发明名称为“新化合物顺-2-（2-呋喃基）-6-苯基四氢吡喃及其制备方法，和其合成中间体及中间体的制备方法”的分案申请。
技术领域
本发明涉及一种中间体化合物及其制备方法，属于手性天然产物的合成领域。
背景技术
顺- 2,6- 二取代四氢吡喃类化合物是许多天然产物的主要结构单元，具有抗过敏、抗癌等多种生物和药理活性。
因而，其合成方法的研究成为有机合成中的一个热点问题，英国剑桥大学的Matthew O’Brien 等给出了一种如下合成路线：
。
发明内容
本发明给出了一种新的顺-2,6-二取代四氢吡喃类化合物；
。
同时进一步给出这一新化合物的合成方法。其是以糠醛、炔丙基溴、苯甲醛为原料，通过醛亲核加成、炔催化氢化以及酸催化环合等一系列反应得到目标产物。具体来说，其合成路线如下：
。
其中在化合物4的制备中，采用5%Pd-C为催化剂。
进一步地，化合物3在全氢气气氛下反应10分钟，制备得到化合物4。
其中，化合物3、4作为合成中间体，均为首次得到，是一种新的化合物。
化合物1和化合物2是现有的化合物，可以根据已知的公开文献制备得到。譬如，（1）Bieber, L. W.; da Silva, M. F.; da Costa, R. C.; Silva,L. O. S. [J].Tetrahedron Lett. 1998, 39, 3655–3658； （2）Petrier,C.; Luche, J.-L. [J]. J.Org. Chem. 1985, 50, 910–912；（3）Makoto, H.; Sakuragi, R.; Okabe, S.; Hosomi,[J]. A.Chem. Commun. 2001, 357–358; 以及（4） Brown, H. C.; Khire,U. R.; Narla,G.; Racherla, U. S. [J]. J. Org. Chem. 1995, 60,545–549.
化合物3的合成过程中，化合物2首先与正丁基锂正己烷反应，而后再与苯甲醛反应得到化合物3。其中化合物2与正丁基锂正己烷的反应温度为-15℃。
本发明给出了一种新的顺-2-（2-呋喃基）-6-苯基四氢吡喃的合成中间体及其合成方法，从而为该类化合物在天然产物和手性药物合成的应用提供了基础。
具体实施方式
为了更好的解释本发明，下面结合实施例对本发明进行进一步的阐述。在本实施例中所用到的仪器、试剂，除非有特殊说明，均为市售产品。
实施例1
在氮气保护下，将400 mg（1.6 mmol）化合物 2溶于5 mL无水四氢呋喃中。使用液氮-甲醇浴将反应液冷却至-78℃后，通过注射器向反应液中逐滴加入0.96 mL正丁基锂的正己烷溶液（2.5M，2.4 mmol）。加入正丁基锂正己烷溶液后，反应液变为墨绿色。继续在-78℃下搅拌反应15 min，然后在-15℃下（冰-丙酮浴冷却）反应45min。将0.244 mL（2.4 mmol）苯甲醛溶于2.5 mL无水四氢呋喃。在将反应液冷却至-78℃后，将苯甲醛的无水四氢呋喃溶液通过注射器逐滴加入反应液中，反应液自然升温至-15℃，此时可观察到反应液呈棕黄色。TLC（V（乙醚）：V（石油醚）= 1 : 3展开）跟踪反应，直至反应完全。撤去冷浴，加入10 mL饱和氯化铵溶液淬灭反应，加入少量蒸馏水溶解产生的沉淀。将反应混合物转移至分液漏斗中，用15 mL×3乙醚萃取，合并有机相，无水硫酸镁干燥，减压蒸除溶剂，得一黄色油状物，787 mg。硅胶柱层析（V（石油醚）：V（乙醚）=1 : 0 → 3 : 1梯度洗脱）分离，得浅黄色油，化合物3，477 mg，产率84%。1H NMR(300 MHz, CDCl3) δ:7.54 (1H, 5'-H), 7.40-7.30(5H, PhH), 6.38(1H, 4'-H), 6.28(1H, 3'-H), 5.46 (1H, 1-H), 4.90 (1H, 5-H),2.85 (2H, 4-H), 0.95 (9H, 3×CH3), 0.10-0.00 (6H, 2×SiCH3)。化合物3经1H NMR 分析,证明与预期结构相符。
实施例2
将100 mg（0.28 mmol）化合物3溶于10 mL乙酸乙酯中。对反应瓶抽真空至溶剂沸腾冒泡，再通入氮气。反复抽真空通氮气操作至少三次以上，保证反应瓶内是完全的氮气气氛后，加入10 mg（0.0047 mmol）5% Pd-C催化剂，继续对反应液边搅拌边抽真空至溶剂沸腾后，再通过氢气球通入氢气。重复抽真空通氢气操作至少三次以上，保证反应瓶内完全充满氢气。在完全氢气气氛下搅拌反应10 min后，拔除氢气球，抽真空，通氮气，反复抽真空通氮气操作三次以上，目的是完全置换出氢气，包括催化剂Pd-C上吸附的氢气，以阻断反应物继续发生氢化反应。通过硅藻土过滤反应液，并用15 mL×3乙酸乙酯洗涤滤饼，合并滤液及洗液，减压蒸除溶剂，得一黄色油，化合物4，97 mg，产率96%。1H NMR(300 MHz, CDCl3) δ:7.40-7.20 (6H, 5'-H, PhH),6.25(1H, 4'-H), 6.10(1H, 3'-H), 4.62 (2H, 1-H, 5-H), 2.15 (2H, CH2), 1.80 (2H, CH2), 1.50-1.20 (2H, CH2), 0.85 (9H, 3×CH3),0.00- -0.10 (6H, 2×SiCH3)。化合物4经1H NMR 分析,证明与预期结构相符。
实施例3
将100 mg（0.277 mmol）化合物4溶于10 mL乙腈，加入20 mg（0.106 mmol）对甲苯磺酸一水合物，室温下搅拌反应。TLC（V（乙醚）：V（石油醚）= 1 : 5展开）跟踪反应，直至反应完全。向反应液中加入二氯甲烷和石油醚，搅拌均匀后，将反应混合物通过盛有硅胶的砂芯漏斗过滤，并用15 mL×3乙醚洗涤滤饼，合并滤液及洗液，减压蒸除溶剂，得一黄色油。硅胶柱层析（V（石油醚）：V（乙醚）=1 : 0 → 15 : 1梯度洗脱）分离，得一无色油，化合物5，58mg，产率92%。1H NMR(300 MHz, CDCl3) δ: 7.35-7.10 (6H, PhH, 5'-H),6.20 (2H, 4'-H,3'-H), 4.60-4.40 (2H, 2-H, 6-H), 2.10-1.50 (6H, 3-H,4-H,5-H)。化合物5经1H NMR分析,证明与预期结构相符。
对比例1
将100 mg（0.28 mmol）化合物3溶于10 mL乙酸乙酯中。对反应瓶抽真空至溶剂沸腾冒泡，再通入氮气。反复抽真空通氮气操作至少三次以上，保证反应瓶内是完全的氮气气氛后，加入10 mg（0.0047 mmol）5% Pd-C催化剂，继续对反应液边搅拌边抽真空至溶剂沸腾后，再通过氢气球通入氢气。重复抽真空通氢气操作至少三次以上，保证反应瓶内完全充满氢气。在完全氢气气氛下搅拌反应2 min后，拔除氢气球，抽真空，通氮气，反复抽真空通氮气操作三次以上，目的是完全置换出氢气，包括催化剂Pd-C上吸附的氢气，以阻断反应物继续发生氢化反应。通过硅藻土过滤反应液，并用15 mL×3乙酸乙酯洗涤滤饼，合并滤液及洗液，减压蒸除溶剂，得到化合物6，结构如下：
。
对比例2
将100 mg（0.28 mmol）化合物3溶于10 mL乙酸乙酯中。对反应瓶抽真空至溶剂沸腾冒泡，再通入氮气。反复抽真空通氮气操作至少三次以上，保证反应瓶内是完全的氮气气氛后，加入10 mg（0.0047 mmol）5% Pd-C催化剂，继续对反应液边搅拌边抽真空至溶剂沸腾后，再通过氢气球通入氢气。重复抽真空通氢气操作至少三次以上，保证反应瓶内完全充满氢气。在完全氢气气氛下搅拌反应30 min后，拔除氢气球，抽真空，通氮气，反复抽真空通氮气操作三次以上，目的是完全置换出氢气，包括催化剂Pd-C上吸附的氢气，以阻断反应物继续发生氢化反应。通过硅藻土过滤反应液，并用15 mL×3乙酸乙酯洗涤滤饼，合并滤液及洗液，减压蒸除溶剂，得到化合物7，结构如下：
。
对比例3
将100 mg（0.28 mmol）化合物3溶于10 mL乙酸乙酯中。对反应瓶抽真空至溶剂沸腾冒泡，再通入氮气。反复抽真空通氮气操作至少三次以上，保证反应瓶内是完全的氮气气氛后，加入10 mg Lindlar催化剂，继续对反应液边搅拌边抽真空至溶剂沸腾后，再通过氢气球通入氢气。重复抽真空通氢气操作至少三次以上，保证反应瓶内完全充满氢气。在完全氢气气氛下搅拌反应2 min后，拔除氢气球，抽真空，通氮气，反复抽真空通氮气操作三次以上，目的是完全置换出氢气，包括催化剂Pd-C上吸附的氢气，以阻断反应物继续发生氢化反应。通过硅藻土过滤反应液，并用15 mL×3乙酸乙酯洗涤滤饼，合并滤液及洗液，减压蒸除溶剂，得到化合物8，结构如下：
。
对比例4
按照实施例3中的反应条件，对与本发明中所用的甲苯磺酸一水合物-乙腈体系催化体系相近的其他催化体系进行考察，以期获得更多的可能性，结果如下：
Claims (2)
1.一种式3所示的中间体化合物，所述该中间体化合物是指顺-2,6-二取代四氢吡喃类化合物制备的中间体化合物：。
2.权利要求1所述的中间体的制备方法，其特征是，化合物3的合成路线如下：
。
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| A diastereoselective route to 2,6-syn-disubstituted tetrahydropyrans:synthesis of the civet compound (+)-2-((2S,6S)-6-methyltetrahydro-2H-pyran-2-yl) acetic acid;Matthew O’Brien等，;《Chem. Commun.》;20090930;第5559-5561页 * |
| Biosynthesis of the Spiroacetal Suite in Bactrocera tryoni;Yvonne K. Booth等，;《ChemBioChem》;20101209;第155-172页，尤其是第157页 * |
| Diastereo- and Enantioselective Iridium-Catalyzed Carbonyl Propargylation from the Alcohol or Aldehyde Oxidation Level:1,3-Enynes as Allenylmetal Equivalents;Laina M. Geary等，;《Angew. Chem. Int. Ed.》;20120215;第2972-2976页 * |
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