CN106588651A - 苯乙烯类季碳化合物及其制备方法 - Google Patents

苯乙烯类季碳化合物及其制备方法 Download PDF

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CN106588651A
CN106588651A CN201611027134.8A CN201611027134A CN106588651A CN 106588651 A CN106588651 A CN 106588651A CN 201611027134 A CN201611027134 A CN 201611027134A CN 106588651 A CN106588651 A CN 106588651A
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钱群
虞盈盈
贾霄
龚和贵
王洪宇
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University of Shanghai for Science and Technology
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Abstract

本发明涉及一种苯乙烯类季碳化合物及其制备方法，该苯乙烯类季碳化合物的结构通式为：其中：R1为C1‑C8烷基链或芳香基团，R2为OMe、CF3等取代基。本发明的反应是金属镍催化还原偶联反应，使用环境友好型的Zn粉为还原剂，价格低廉且价态稳定的溴化镍乙二醇二甲醚（NiBr2.glyme）作催化剂。这类反应条件温和，操作简单，对官能团的适应性好，产率普遍较高，而且三级卤代底物无异构化副产物生成。

Description

苯乙烯类季碳化合物及其制备方法
技术领域
本发明是涉及一种苯乙烯类季碳化合物及其制备方法，特别是一种镍催化三级卤代烷烃还原偶联构建C(sp3)-C(sp3)季碳化合物及其制备方法。
背景技术
碳-碳键是化学中最基本的一种化学键，碳-碳键形成方法的发展，推动着有机合成化学发展的进程，因而，如何高效的构建新的碳-碳键，显得尤为重要，更是吸引了无数科研工作者的关注。Wittig反应、Diels-Alder反应、格氏反应等一系列经典的碳-碳键成键反应的发现与应用在有机合成中扮演了举足轻重的角色。近几十年以来,随着过渡金属催化有机反应的蓬勃发展,它们“魔术”般的催化效果为一些在通常情况下难以合成的碳-碳键架起了桥梁，逐渐成为当代有机合成的最重要手段之一。
烷基类化合物的烯丙基化反应是现代有机合成化学中一类重要的反应类型，有着广泛的应用价值。该类反应具有三个显著的特点：(1)通用性强：烯丙基金属配合物既可以与亲电试剂反应，也可以与亲核试剂反应；(2)反应条件温和：烯丙基化合物形成金属配合物后，其双键的反应活化能大大降低；(3)化学区域和立体选择性多变：随着不同中心金属及手性配体的改变，区域和立体选择性可以根据特定的要求和用途进行调控。
季碳化合物的合成在有机化学中极具挑战性，在材料化学和药物分子领域等也有良好的应用前景。如天然化合物(-)-asperazine和(-)hodgkinsine是具有抗菌、抗病毒及细胞毒素效应的生物活性分子。因而，如何高效合成季碳化合物显得非常重要。迄今为止，季碳化合物依然很难合成，即使在过渡金属催化方面，对于三级底物的开发也鲜见报道：一方面是三级底物位阻较大，不易与金属有效“亲近”，另一方面，三级底物在参与到某些反应中时(比如自由基机理的反应)，会出现异构化副产物，导致期望得到的目标产物难以分离提纯，使合成反应的应用价值大打折扣。常见金属催化反应类型有Kumada，Negishi，Stille等偶联反应。但这些方法都需要预先制备有机金属试剂R-MX。由于R-MX高活性，保存和反应条件苛刻(无水无氧以及低温)，易发生副反应(如β-氢消除)，且底物适应性差(如含2-位的OR基团的原料很难制备)，使得它的实用性受到很大限制。由此可见，开发三级卤代烷烃合成季碳化合物具有很大的挑战性，在实际合成应用和学术理论研究方面具有重要的意义。
发明内容
本发明的目的之一在于提供一种苯乙烯类季碳化合物。
本发明的目的之二在于该苯乙烯类季碳化合物的制备方法。
为达到上述目的，本发明采用如下反应机理：
其中：R1为C1-C8烷基链或芳香基团，R2为甲氧基或三氟甲基。
一种苯乙烯类季碳化合物，其特征在于该苯乙烯类季碳化合物的结构通式为：
其中：R1为C1-C8烷基链或芳香基团，R2为甲氧基或三氟甲基。
一种制备上述的苯乙烯类季碳化合物的方法，在Ni/Zn还原偶联反应体系下实现高效的偶联，其特征在于该方法的具体步骤为：在装有磁子干燥的Schlenk反应瓶中加入Zn粉，2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶，MgCl2，抽真空充氮气三次后，加入溴化镍乙二醇二甲醚，然后注入碳酸2-(4-取代苯基)烯丙酯甲酯A，三级卤代烷烃B，吡啶和溶剂N,N-二甲基乙酰胺；反应在氮气保护下于20～25℃，搅拌8～12h，经分离提纯后得到后得到苯乙烯类季碳化合物；所述的碳酸2-(4-取代苯基)烯丙酯甲酯A、三级卤代烷烃B、吡啶、Zn粉、2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶、MgCl2和溴化镍乙二醇二甲醚的摩尔比为：(1.5-2.5)∶1∶0.3∶3∶0.15∶1∶0.1；所述的碳酸2-(4-取代苯基)烯丙酯甲酯A的结构为：所述的三级卤代烷烃B的结构通式为：
本发明中所述的苯乙烯类季碳化合物1可以是：
本发明的反应体系是金属催化还原偶联，使用环境友好型的Zn粉为还原剂，价格低廉且价态稳定的溴化镍乙二醇二甲醚(NiBr2.glyme)作催化剂。
为弥补合成上不足，本文开发了镍催化三级卤代烷烃与碳酸2-(4-取代苯基)烯丙酯甲酯进行还原交叉偶联的烯丙基化反应，构建C(sp3)-C(sp3)季碳化合物的方法。因在反应过程中不需要预先制备有机金属亲核试剂，提高了合成效率，且不涉及转金属步骤，因此反应机理与传统偶联方式有所不同。最后，由于有机亲电试剂一般易于得到、操作便利且一般较稳定，采用亲电试剂/亲电试剂直接偶联使反应底物的选择更加灵活多样。
本发明成功开发了镍催化三级卤代烷烃与碳酸2-(4-取代苯基)烯丙酯甲酯还原交叉偶联的烯丙基化反应，构建C(sp3)-C(sp3)季碳化合物的方法。这类反应条件温和，操作简单，对官能团的适应性好，产率普遍较高，而且三级底物无异构化副产物生成。
具体实施方式
实例1：1-(4,4-二甲基辛基-1-烯-2-基)-4-(三氟甲基)苯
1-(4,4-dimethyloct-1-en-2-yl)-4-(trifluoromethyl)benzene
在干燥装有磁子的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入溶剂N,N-二甲基乙酰胺(DMA,1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-(4-(trifluoromethyl)phenyl)vinyl)carbonate,液体,0.6mmol,200％)，三级卤代烃(2-bromo-2-methylhexane,液体,0.3mmol,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(63.0mg,0.222mmol,74％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ7.57(d,J＝8.2,2H),7.49(d,J＝8.1,2H),5.31(d,J＝1.8,1H),5.13(s,1H),2.50(s,2H),1.24–1.09(m,6H),0.85(t,J＝6.8,3H),0.76(s,6H).13C NMR(125MHz,CDCl3):δ147.70,146.54,129.17,127.57,125.42,125.03,118.29,46.83,42.31,27.60,26.34,23.48,23.41,14.06.
实例2：(4,4-二甲基辛基-1-烯-2-基)苯
(4,4-dimethyloct-1-en-2-yl)benzene
在装有磁子干燥的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入溶剂DMA(1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-phenylvinyl)carbonate,液体,0.6mmol,200％)，三级卤代烷烃(2-bromo-2-methylhexane,液体,0.3mmol,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(55.1mg,0.255mmol,85％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ7.49–7.47(m,2H),7.40–7.37(m,2H),7.34–7.31(m,1H),5.35(d,J＝2.1,1H),5/14-5.13(m,1H),2.58(s,2H),1.31–1.22(m,6H),0.96(t,J＝6.9,3H),0.87(s,6H).13C NMR(125MHz,CDCl3):δ147.58,144.00,128.03,126.85,126.57,116.46,46.91,42.35,34.14,27.65,26.36,23.51,14.15.HRMS(ESI)m/z(M+)calcd for C16H24:216.19508,found:216.19471.
实例3：3,3-二甲基-5-苯己基-5-烯-1-基苯甲酸酯
3,3-dimethyl-5-phenylhex-5-en-1-yl benzoate
在装有磁子干燥的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入溶剂DMA(1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-phenylvinyl)carbonate,0.6mmol,液体,200％)，三级卤代烷烃(3-bromo-3-methylbutyl benzoate,液体,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(78.5mg,0.255mmol,85％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ8.10–8.05(m,2H),7.60–7.53(m,1H),7.49–7.39(m,4H),7.36–7.31(m,2H),7.29–7.23(m,1H),5.34(d,J＝2.0,1H),5.13–5.11(m,1H),4.39(t,J＝7.3,2H),2.61(s,2H),1.73(t,J＝7.3,2H),0.91(s,6H).13CNMR(125MHz,CDCl3):δ166.42,146.66,143.42,132.63,130.35,129.37,128.16,128.08,126.97,126.38,117.01,62.13,47.34,40.19,33.55,27.59.
实例4：(3,3-二甲基己基-5-烯-1,5-二基)二苯
(3,3-dimethylhex-5-ene-1,5-diyl)dibenzene
在装有磁子干燥的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入溶剂DMA(1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-phenylvinyl)carbonate,0.6mmol,液体,200％)，三级卤代烷烃((3-bromo-3-methylbutyl)benzene,液体,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(65.8mg,0.249mmol,83％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ7.55–7.50(m,2H),7.46–7.41(m,2H),7.41–7.33(m,3H),7.31–7.25(m,1H),7.178–7.12(m,2H),5.39(d,J＝2.0,1H),5.21–5.19(m,1H),2.69(s,2H),2.67–2.62(m,2H),1.62–1.56(m,2H),0.98(s,6H).13C NMR(125MHz,CDCl3):147.27,143.89,143.26,128.23,128.19,128.15,126.96,126.59,125.44,116.85,46.62,44.60,34.37,30.74,27.74.
实例5：(2,2-二甲基戊基-4-烯-1,4-二基)二苯
(2,2-Dimethylpent-4-ene-1,4-diyl)dibenzene
在装有磁子干燥的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入DMA(1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-phenylvinyl)carbonate,0.6mmol,液体,200％)，三级卤代烷烃((2-bromo-2-methylpropyl)benzene,液体,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(55.5mg,0.222mmol,74％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ7.54–7.48(m,2H),7.44–7.29(m,6H),7.22–7.20(m,2H),5.42(d,J＝2.0,1H),5.22–5.17(m,1H),2.69(s,2H),2.62(s,2H),0.86(s,6H),13C NMR(125MHz,CDCl3):δ147.06,143.71,139.10,130.64,128.13,127.56,126.96,126.47,125.74,116.91,49.62,47.98,35.40,26.84.
实例6:1-(4,4-二甲基-1-烯-6-苯基-己基)-4-甲氧基-苯
1-(4,4-Dimethyl-1-ene-6-phenyl-hexyl)-4-methoxy-benzene
在装有磁子干燥的Schlenk反应瓶中加入Zn粉(0.9mmol,300％)，配体2,6-二-(4-异丙基-4,5-二氢恶唑-2-基)吡啶(iPr-box,0.045mmol,15％)，MgCl2(0.3mmol,100％)。盖上橡皮塞反复抽真空冲氮气三次后，在手套箱里面加入溴化镍乙二醇二甲醚(NiBr2.Glyme,0.03mmol,10％)，然后注入溶剂DMA(1ml)，碳酸2-(4-取代苯基)烯丙酯甲酯(methyl(1-phenylvinyl)carbonate,0.6mmol,液体,200％)，三级卤代烷烃((3-bromo-3-methyl butyl)benzene液体,100％)，吡啶(0.09mmol,30％)。反应在氮气保护下于20-25℃搅拌8-12h。反应结束后，直接通过柱层析分离后得到目标产物(76.8mg,0.261mmol,87％产率)。
该产物为无色油状液体。1H NMR(500MHz,CDCl3):δ7.44(d,J＝8.8,2H),7.35(t,J＝7.4,2H),7.26(t,J＝7.1,1H),7.16(d,J＝7.2,2H),6.96(d,J＝8.2,2H),5.33(d,J＝1.9,1H),5.12(s,1H),3.89(s,3H),2.69–2.61(m,4H),1.62–1.56(m,2H),0.97(s,6H).13CNMR(125MHz,CDCl3):δ158.73,146.50,143.22,136.23,128.18,128.12,127.55,125.37,115.40,113.43,55.05,46.56,44.57,34.26,30.68,27.70.HRMS(ESI)m/z(M+)calcd forC21H26O:294.20564,found:294.20545.
综上实验结果可见：采用本发明所述的镍催化三级卤代烷烃与碳酸2-(4-取代苯基)烯丙酯甲酯的还原偶联反应可以在温和、操作简单的条件下高效的合成C(sp3)-C(sp3)季碳化合物，而且三级底物无异构化副产物生成。
最后有必要在此说明的是：上述实施例是用于对本发明的技术方案作进一步详细地说明，本领域的技术人员根据本发明的上述实施例及实验方法均属于本发明的保护范围。

Claims (2)

1.一种苯乙烯类季碳化合物，其特征在于该苯乙烯类季碳化合物的结构通式为：
其中：R1为C1-C8烷基链或芳香基团，R2为甲氧基或三氟甲基。
2.一种制备根据权利要求1所述的苯乙烯类季碳化合物的方法，在Ni/Zn还原偶联反应体系下实现高效的偶联，其特征在于该方法的具体步骤为：在装有磁子干燥的Schlenk反应瓶中加入Zn粉，2,6-二-（4-异丙基-4,5-二氢恶唑-2-基）吡啶，MgCl2，抽真空充氮气三次后，加入溴化镍乙二醇二甲醚，然后注入碳酸2-（4-取代苯基）烯丙酯甲酯A，三级卤代烷烃B，吡啶和溶剂N,N-二甲基乙酰胺；反应在氮气保护下于20～25 oC，搅拌8～12h，经分离提纯后得到后得到苯乙烯类季碳化合物；所述的碳酸2-（4-取代苯基）烯丙酯甲酯A、三级卤代烷烃B、吡啶、Zn粉、2,6-二-（4-异丙基-4,5-二氢恶唑-2-基）吡啶、MgCl2和溴化镍乙二醇二甲醚的摩尔比为：（1.5-2.5）：1：0.3：3：0.15：1：0.1；所述的碳酸2-（4-取代苯基）烯丙酯甲酯A的结构为：；所述的三级卤代烷烃B的结构通式为：。
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