CN112125800A - 钯催化的硫叶立德与溴代物的卡宾偶联反应用于合成三取代的烯烃 - Google Patents
钯催化的硫叶立德与溴代物的卡宾偶联反应用于合成三取代的烯烃 Download PDFInfo
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 18
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 4
- 230000002194 synthesizing effect Effects 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 17
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
本发明涉及一种钯催化的硫叶立德与溴代物的卡宾偶联反应,通过该方法可以合成得到一系列三取代的烯烃。该方法采用安全、稳定,且容易制备的硫叶立德作为卡宾偶联反应的亲核试剂,在构建取代的碳碳双键领域具有良好的适用性。
Description
技术领域
涉及一种钯催化的硫叶立德与溴代物的卡宾偶联反应构建C=C键,合成三取代的烯烃的合成新方法,属于有机化学技术领域。
背景技术
过去几十年以来,过渡金属催化的偶联反应已经成为构建C-C键和C-N键最有效的方法之一1。一般来说,一个偶联反应的反应底物包括一个亲核试剂和一个亲电试剂。其中,碳碳不饱和键以及金属有机物作为亲核试剂已经被广泛应用,比如赫克反应2、根岸偶联反应3、铃木-宫浦偶联反应4、熊田偶联反应5、施蒂勒反应6、桧山偶联反应7等。在偶联反应领域,虽然亲电试剂仍然主要是卤代物或者其类似物,但是亲核试剂的研究一直是偶联反应领域的主要工作之一8。过去二十年,金属卡宾以一种独特的插入迁移的机理引入到了卡宾偶联反应9。包括重偶氮化合物、腙、联烯、炔、环丙烯和含氮杂环在内的卡宾前体已经被开发作为卡宾偶联反应的亲核试剂9,10。然而,尽管硫叶立德已成为重氮化合物的稳定易得的卡宾替代品,但它的交叉偶联反应的研究却依旧较少11。
另一方面,烯烃的合成由于其独特的性质引起了人们的广泛关注。烯烃复分解反应、维蒂希反应一直是最重要和最常用的方法12。此外,卡宾偶联反应也已经成功开发为构建碳碳双键的新方法,但是目前所使用的卡宾前体主要是不稳定且容易爆炸的重氮化合物。为了避免重氮化合物的使用,因此我们报道了一种钯催化的硫叶立德与溴代物的卡宾偶联反应构建C=C键,合成三取代烯烃的合成新方法。
发明内容
针对现存的通过卡宾偶联反应构建碳碳双键的方法存在的各种问题,本发明的目的是为了提供一种钯催化的硫叶立德的卡宾偶联反应用于构建碳碳双键,该方法是一种温和的替代传统的方法,原料稳定且容易得到、具有广阔的应用前景。
为实现上述目的,本发明采用以下技术方案:
以硫叶立德化合物和溴代物为起始原料,其化学反应式如下所示:
其中:
R1为甲基、甲氧基、氰基、异丙基、卤素、叔丁基等基团。
R2为甲基、乙基、异丙基等基团。
R3为苯基、萘基、呋喃基、乙烯基、丙烯基、己烯基、1,3-二烯基等基团中的一种。
其制备步骤如下:
在氩气保护下,在洁净的反应器中依次加入硫叶立德化合物、溴代物、催化剂、配体、碱和溶剂,放入80℃油浴中反应24h。
反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得产品。
其特征在于催化剂为四(三苯基)膦钯、双(二亚苄基丙酮)钯(0)、醋酸钯、二(三苯基膦)氯化钯、1,1'-双(二苯基膦)二茂铁氯化钯二氯甲烷复合物、三(二亚苄基丙酮)二钯(0)中的一种;配体为三(2-呋喃基)膦、1,1'-双(二苯基膦)二茂铁、三环己基膦四氟硼酸盐、2-二环己基磷-2,4,6-三异丙基联苯、2-(二环己基膦)-3,6-二甲氧基-2',4',6'-三异丙基-11'-联苯中的一种或者几种;碱为叔丁醇锂、叔丁醇钠、三乙胺、碳酸钾、碳酸铯、特戊酸钠、醋酸钾、氢氧化钾、碳酸钠中的两种;溶剂为甲苯、苯、氯苯、四氢呋喃、1,2-二氯乙烷、二甲基亚砜中的一种。步骤(1)中硫叶立德化合物:溴代物:催化剂:配体:碱1:碱2的摩尔比为1:(1.0-2.0):(0.025-0.1):(0.025-0.2):(1.0-3.0):(0.25-0.1)。
本发明采取以上技术方案,其具有以下优点:相比于传统的卡宾偶联反应需要不稳定且容易爆炸的重氮化合物的问题,本发明原料稳定且易得,是一种温和的替代传统的卡宾偶联反应的方法,具有广阔的应用前景。
核磁共振氢谱(1H NMR)、碳谱(13C NMR)以及高分辨质谱证实了合成的烯烃的结构。其中核磁共振图采用Varian INOVA-400 型核磁共振仪测定,以四甲基硅烷(TMS)为内标(δ 0 ppm),氘代氯仿为溶剂;高分辨质谱用 Agilent 1946B 质谱仪测定。
具体实施方法
下面结合具体实施方式对本发明作进一步描述,有助于对本发明的理解。但并不能以此来限制本发明的权利范围,而本发明的权利范围应以权利要求书阐述的为准。
实施案例1:化合物1的合成
(1) 氩气条件下,在洁净的反应器中依次加入α-苯基-α'-乙氧羰基硫叶立德(24 mg,0.1 mmol)、苄溴(25.4 mg,0.15 mmol)、醋酸钯(0.6 mg, 0.0025 mmol)、三(2-呋喃基)膦(0.58 mg, 0.0025 mmol)和叔丁醇锂(16 mg,0.2 mmol)、三乙胺(5.0 mg,0.05 mmol)、甲苯(1 ml),置于80℃油浴中搅拌24h。
(2) 反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得无色液体,收率为87%。1H NMR (400 MHz, Chloroform-d) δ 7.84 (s, 1H), 7.41 – 7.33 (m, 3H),7.25 – 7.13 (m, 5H), 7.08 – 7.03 (m, 2H), 4.28 (q, J = 7.1 Hz, 2H), 1.30 (t,J = 7.1 Hz, 3H); 13C NMR (101 MHz, Chloroform-d) δ 167.94, 140.20, 136.07,134.87, 133.02, 130.68, 129.94, 129.05, 128.67, 128.29, 127.86, 61.30, 14.41.HRMS (ESI): m/z计算值C17H17O2 +: 253.1223,实测值: 253.1224。
实施案例2:化合物2的合成
(1) 氩气条件下,在洁净的反应器中依次加入α-对甲苯基-α'-乙氧羰基硫叶立德(25.4 mg,0.1 mmol)、苄溴(25.4 mg,0.15 mmol)、双(二亚苄基丙酮)钯(0)(1.43 mg,0.0025 mmol)、2-二环己基磷-2,4,6-三异丙基联苯(2.38 mg,0.005 mmol)和叔丁醇锂(16mg,0.2 mmol)、三乙胺(5.0 mg,0.05 mmol)、甲苯(1 ml),置于80℃油浴中搅拌24h。
(2) 反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得无色液体,收率为64%。1H NMR (400 MHz, Chloroform-d) δ 7.80 (s, 1H), 7.22 – 7.13 (m, 5H),7.12 – 7.04 (m, 4H), 4.26 (q, J = 7.1 Hz, 2H), 2.38 (s, 3H), 1.30 (t, J = 7.1Hz, 3H);13C NMR (101 MHz, Chloroform-d) δ 168.18, 139.95, 137.59, 135.03,132.96, 132.94, 130.68, 129.79, 129.45, 128.97, 128.28, 61.29, 21.51, 14.44.HRMS (ESI): m/z计算值C18H19O2 +: 267.1380, 实测值: 267.1385。
实施案例3:化合物3的合成
(1) 氩气条件下,在洁净的反应器中依次加入α-对甲苯基-α'-异丁氧羰基硫叶立德(26.8 mg,0.1 mmol)、苄溴(25.4 mg,0.15 mmol)、醋酸钯(0.6 mg, 0.0025 mmol)、三(2-呋喃基)膦 (0.58 mg, 0.0025 mmol)和碳酸钾(27.6 mg,0.2 mmol)、三乙胺(5.0 mg,0.05mmol)、甲苯(1 ml),置于80℃油浴中搅拌24h。
(2) 反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得无色液体,收率为65%。1H NMR (400 MHz, Chloroform-d) δ 7.84 (s, 1H), 7.42 – 7.28 (m, 4H),7.23 – 7.10 (m, 4H), 7.05 (d, J = 7.0 Hz, 2H), 3.98 (d, J = 6.4 Hz, 2H), 1.99– 1.86 (m, 1H), 0.88 (d, J = 6.8 Hz, 6H); 13C NMR (101 MHz, Chloroform-d) δ167.96, 140.18, 136.14, 134.80, 133.00, 130.72, 129.83, 129.08, 128.63,128.29, 127.79, 71.31, 27.90, 19.18. HRMS (ESI): m/z计算值C19H21O2 +: 281.1536,实测值: 281.1537。
实施案例4:化合物4的合成
(1) 氩气条件下,在洁净的反应器中依次加入α-对甲苯基-α'-乙氧羰基硫叶立德(18.1 mg,0.1 mmol)、烯丙基溴(25.4 mg,0.15 mmol)、醋酸钯(0.6 mg, 0.0025 mmol)、三(2-呋喃基)膦 (0.58 mg, 0.0025 mmol)和叔丁醇锂(16 mg,0.2 mmol)、三乙胺(5.0 mg,0.05 mmol)、乙腈(1 ml),置于80℃油浴中搅拌24h。
(2) 反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得无色液体,收率为55%。1H NMR (400 MHz, Chloroform-d) δ 7.43 (d, J = 11.4 Hz, 1H), 7.42 –7.30 (m, 3H), 7.22 (d, J = 6.5 Hz, 2H), 6.46 – 6.33 (m, 1H), 5.66 (dd, J =17.0, 1.8 Hz, 1H), 5.41 (dd, J = 10.0, 1.8 Hz, 1H), 4.24 (q, J = 7.1 Hz, 2H),1.29 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, Chloroform-d) δ 167.52, 140.46,135.08, 133.70, 133.41, 130.30, 128.05, 127.84, 125.61, 61.17, 14.41. HRMS(ESI): m/z计算值C13H15O2 +: 203.1067, 实测值: 203.1068。
实施案例5:化合物5的合成
(1) 氩气条件下,在洁净的反应器中依次加入α-对甲苯基-α'-乙氧羰基硫叶立德(18.1 mg,0.1 mmol)、对溴溴苄(37.5 mg,0.15 mmol)、醋酸钯(0.6 mg, 0.0025 mmol)、2-(二环己基膦)-3,6-二甲氧基-2',4',6'-三异丙基-11'-联苯(1.34 mg,0.0025 mmol)和叔丁醇锂(16 mg,0.2 mmol)、三乙胺(5.0 mg,0.05 mmol)、甲苯(1 ml),置于80℃油浴中搅拌24h。
(2) 反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得无色液体,收率为55%。1H NMR (400 MHz, Chloroform-d) δ 7.74 (s, 1H), 7.36 (dd, J = 5.3, 2.0Hz, 3H), 7.30 – 7.25 (m, 2H), 7.23 – 7.15 (m, 2H), 6.89 (d, J = 8.3 Hz, 2H),4.26 (q, J = 7.1 Hz, 2H), 1.29 (t, J = 7.1 Hz, 3H); 13C NMR (151 MHz,Chloroform-d) δ 167.70, 138.82, 135.64, 133.78, 133.75, 132.06, 131.56,129.79, 128.82, 128.11, 123.34, 61.45, 14.39. HRMS (ESI): m/z计算值C17H16BrO2 +:331.0328, 实测值: 331.0331。
参考文献
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Claims (7)
2.根据权利要求1所述的方法,其特征在于采用如下制备步骤:
在氩气保护下,在洁净的反应器中依次加入硫叶立德化合物、溴代物、催化剂、配体、碱和溶剂,放入80℃油浴中反应24h;
反应结束后,减压除去溶剂,残留物采用硅胶柱层析纯化即得产品。
3.根据权利要求2所述的制备方法,其特征在于催化剂为四(三苯基)膦钯、双(二亚苄基丙酮)钯(0)、醋酸钯、二(三苯基膦)氯化钯、1,1'-双(二苯基膦)二茂铁氯化钯二氯甲烷复合物、三(二亚苄基丙酮)二钯(0)中的一种。
4.根据权利要求2所述的制备方法,其特征在于配体为三(2-呋喃基)膦、1,1'-双(二苯基膦)二茂铁、三环己基膦四氟硼酸盐、2-二环己基磷-2,4,6-三异丙基联苯、2-(二环己基膦)-3,6-二甲氧基-2',4',6'-三异丙基-1,1'-联苯中的一种或者几种。
5.根据权利要求2所述的制备方法,其特征在于碱为叔丁醇锂、叔丁醇钠、三乙胺、碳酸钾、碳酸铯、特戊酸钠、醋酸钾、氢氧化钾、碳酸钠中的两种。
6.根据权利要求2所述的制备方法,其特征在于溶剂为甲苯、苯、氯苯、四氢呋喃、1,2-二氯乙烷、二甲基亚砜中的一种。
7.根据权利要求2所述的制备方法,步骤(1)中硫叶立德化合物:溴代物:催化剂:配体:碱1:碱2的摩尔比为1:(1.0-2.0):(0.025-0.1):(0.025-0.2):(1.0-3.0):(0.25-0.1)。
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