CN110590821A - 铱催化的硫叶立德作为卡宾前体的B-H键插入反应合成α-硼代羰基化合物 - Google Patents
铱催化的硫叶立德作为卡宾前体的B-H键插入反应合成α-硼代羰基化合物 Download PDFInfo
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- 238000006713 insertion reaction Methods 0.000 title claims abstract description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000002243 precursor Substances 0.000 title claims abstract description 5
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
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- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000002541 furyl group Chemical group 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 125000001544 thienyl group Chemical group 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
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- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
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- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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Abstract
本发明涉及一种铱催化的、硫叶立德作为卡宾前体与路易斯碱硼烷加成物的B‑H插入反应高效合成α‑硼代羰基化合物的方法。与其他方法相比，本方法原料稳定易得、步骤简单、条件温和，是一种有效制备有机合成中重要的分子实体——α‑硼代羰基化合物的方法，具有广阔的应用前景。
Description
技术领域
本发明涉及一种Ir催化的、硫叶立德作为卡宾前体与路易斯碱硼烷加成物的B-H插入反应温和、高效的合成有机合成中重要的分子实体——α-硼代羰基化合物，属于化学合成领域。
背景技术
有机硼化合物在医药、材料化学、有机合成等领域有着广泛的应用，并且已报道了几种有效的方法来构建C-B键1-4。其中， α-硼代羰基化合物由于其两性特性，最近被认为是重要的有机合成分子实体5。然而，到目前为止合成稳定、可分离的α-硼代羰基化合物的方法报道较少，有关的几个方法都有着低收率、恶劣的条件和步骤繁琐的缺点6-9。因此，发展高效、简单的羰基α-硼代羰基化合物合成方法仍然亟待开发。最近，有报道科学家利用过渡金属催化的α-重氮羰基化合物与硼烷加合物的合成，做为一个有效的替代合成α-硼代羰基化合物的方法10-13。然而，重氮化合物有毒、不稳定，具潜在的爆炸性。此后，周其林的研究小组又开发了一种高效的金催化末端炔与硼烷加合物氧化偶联反应的方法14。但由于原子利用率低，催化剂在商业上难以获得，因此其实用性有限。最近，Curran小组报道了一个全新的方法来制备该类化合物。该方法通过NHC-硼烷络合物与烯基三氟甲磺酰酯反应得到α-硼代羰基化合物15。在这一过程中，不需要催化剂和传统的高能引发剂，但分离收率通常较低。因而开发经济、高效、安全的方法来制备α-硼代羰基化合物一项具有重大意义的研究。硫叶立德类化合物安全、稳定、易于制备(从相应的羧酸中得到)，因此自从硫叶立德化合物被证明是重氮化合物的替代金属卡宾类化合物以来，先后报道了包括插入反应、C-H活化在内的许多反应被16。本发明提供了一种以硫叶立德为起始原料，与路易斯碱硼烷加成物通过铱催化的B-H卡宾插入反应，简单高效的合成α-硼代羰基化合物的新方法。
发明内容
本发明实现了以硫叶立德为卡宾试剂，1,5-环辛二烯氯化铱二聚体作为催化剂，通过B-H键插入反应高效合成α-硼代羰基化合物。解决了此前报道的各种方法中步骤繁琐、条件苛刻、原料不稳定、收率低、催化剂昂贵、原子利用率低等问题。本发明的原料易得（从相应的羧酸得到），底物适用性好，是一种温和、快速、简单、有效的制备α-硼代羰基化合物的方法，具有广阔的应用前景。
本发明的化学反应式如下所示：
。
（1）在洁净的反应瓶中依次加入硫叶立德化合物、路易斯碱硼烷加成物、催化剂、添加剂、溶剂，移到60℃中搅拌3h。
（2）TLC检测反应结束后，湿法过柱，残留物采用硅胶柱层析分离纯化即得产品。
（3）步骤（1）中的添加剂为二氟化铜、氰化亚铜、醋酸铜、氟化铜、醋酸银、氯化锌、醋酸铑、氯化亚铜、三氯化铁、溴化铜、双三氟甲烷磺酸锌、双三氟甲烷磺酸铜、氯化铜中的一种或一种以上。步骤（1）中的溶剂为1，2-二氯乙烷、氯苯、二氯甲烷、氯仿、1，4-二氧六环、乙腈中的一种或一种以上。步骤（1）中的硫叶立德类化合物：路易斯碱硼烷加成物：催化剂：添加剂的摩尔比为1：（2.0~4.0）：（0.025~0.2）：（0.05~2.0）。
用核磁共振氢谱（1H NMR）、碳谱（13C NMR）、硼谱（11B NMR）以及高分辨质谱证实了结构的正确性。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；硼谱用三氟化硼乙醚络合物作为外标（δ 0ppm）；高分辨质谱用 Agilent 1946B 质谱仪测定。
具体实施方式
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
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、硼烷加合物 (0.6mmol)、[Ir(COD)Cl]2 (5 mol %)和CuF2 (20 mol %)。然后加入10ml PhCl, 60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到白色固体，熔点为59-61℃，收率94％。
1 (400 MHz, Chloroform-d) δ 8.00 (d, J = 7.2 Hz, 2H), 7.47 (t, J =7.2 Hz, 1H), 7.40 (t, J = 7.2 Hz, 2H), 2.61 (s, 9H), 2.46 (t, J = 5.2 Hz,2H); 13C NMR (101 MHz, Chloroform-d) δ 208.09, 138.12, 131.84, 128.79, 128.13,52.29, 29.84; 11B NMR (128 MHz, Chloroform-d) δ -3.74 (t, J B-H = 101.9 Hz);HRMS (ESI)m/z计算值 [C11H18BNNaO, M + Na] + : 214.0708; 实测值: 214.0710。
实施案例2：化合物2的合成
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、硼烷加合物 (0.6mmol)、[Ir(COD)Cl]2 (5 mol %)和CuF2 (20 mol %)。然后加入10ml PhCl, 60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到白色固体，熔点为64-65℃，收率81％
1H NMR (400 MHz, Chloroform-d) δ 7.50 (dd, J = 1.6, 0.8 Hz, 1H), 7.09(dd, J = 3.6, 0.8 Hz, 1H), 6.45 (dd, J = 3.6, 1.6 Hz, 1H), 2.61 (s, 9H), 2.30(t, J = 5.2 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) δ 197.15, 153.66, 145.15,116.16, 111.67, 52.34, 29.84; 11B NMR (128 MHz, Chloroform-d) δ -3.10 (t, J B-H= 103.0 Hz); HRMS (ESI)m/z计算值 [C9H16BNNaO2, M + Na] + : 204.1172; 实测值:224.1175。
实施案例3：化合物3的合成
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、硼烷加合物 (0.6mmol)、[Ir(COD)Cl]2 (20 mol %)和CuF2 (2.0 eq)。然后加入10ml PhCl, 60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到白色固体，熔点为45-47℃，收率97％。
1 (400 MHz, Chloroform-d) δ 2.57 (s, 9H), 1.96 (d, J = 5.2 Hz, 2H),1.83 – 1.60 (m, 8H), 1.34 – 1.26 (m, 3H), 1.24 – 1.17 (m, 2H).13C NMR (101MHz, Chloroform-d) δ 222.18, 52.33, 49.85, 29.84, 29.34, 26.24, 26.16; 11B NMR(128 MHz, Chloroform-d) δ -4.52 (t, J B-H = 101.3 Hz); HRMS (ESI)m/z计算值[C11H24BNNaO, M + Na] + :220.1849; 实测值: 220.1845。
实施案例4：化合物4的合成
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、三甲基氨基硼烷络合物 (0.6 mmol)、[Ir(COD)Cl]2 (5 mol %)和碘化亚铜(20 mol％)。然后加入10mL PhCl,60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到白色固体，熔点为85-87℃，收率45％。1H NMR (400 MHz, Chloroform-d) δ7.99 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), 2.61 (s,9H), 2.42 (t, J = 5.2 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) δ 207.00,162.56, 131.20, 130.98, 113.24, 55.47, 52.30, 29.84; 11B NMR (128 MHz,Chloroform-d) δ -3.54 (t, J B-H = 99.8 Hz); HRMS (ESI) m/z计算值 [C12H20BNNaO2, M+ Na] + : 244.1485; 实测值: 244.1485。
实施案例5：化合物5的合成
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、三甲基氨基硼烷络合物 (0.6 mmol)、[Ir(COD)Cl]2 (5 mol %)和氟化铜(20 mol％)。然后加入10mL DCE, 60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到白色固体，熔点为81-83℃，收率80％。1H NMR (400 MHz, Chloroform-d) δ 8.55(s, 1H), 8.09 (d, J = 8.4 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 8.4Hz, 2H), 7.51 (m, 2H), 2.63 (s, 9H), 2.59 (m, 2H); 13C NMR (101 MHz,Chloroform-d) δ 208.15, 135.43, 135.24, 132.83, 130.07, 129.73, 127.74 (2 C),127.71, 126.25, 125.21, 52.32, 29.84; 11B NMR (128 MHz, Chloroform-d) δ -3.62(t, J B-H = 107.8 Hz); HRMS (ESI)m/z计算值[C15H20BNNaO, M + Na] + : 264.1536; 实测值: 264.1540。
实施案例6：化合物6的合成
在装有磁性搅拌子的25 mL玻璃瓶中加入硫叶立德(0.15 mmol)、N-甲基吡咯烷硼烷络合物 (0.6 mmol)、[Ir(COD)Cl]2 (5 mol %)和氟化铜(20 mol％)。然后加入10mL PhCl,60℃搅拌3h，TLC检测反应完全后。然后用EA稀释，减压除去溶剂，采用PE/EA硅胶层析法分离纯化得到淡黄色液体，收率68％。1H NMR (400 MHz, Chloroform-d) δ 8.03 – 7.98(m, 2H), 6.91 – 6.87 (m, 2H), 3.84 (s, 3H), 3.21 – 3.10 (m, 2H), 2.89 – 2.80(m, 2H), 2.64 (s, 3H), 2.43 (t, J = 5.2 Hz, 2H), 2.04 – 1.89 (m, 5H);13C NMR(101 MHz, Chloroform-d) δ 207.23, 162.51, 131.22, 130.95, 113.22, 61.56,55.46, 47.90, 29.84, 22.60; 11B NMR (128 MHz, Chloroform-d) δ -4.83 (t, J B-H =101.8 Hz); HRMS (ESI)m/z计算值 [C13H20BNNaO2, M + Na] + : 256.1485; 实测值:256.1487。
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Claims (5)
1.一种基于铱催化剂催化的路易斯碱硼烷加成物的B-H键插入反应高效合成α-硼代羰基化合物的新方法，其特征在于以硫叶立德化合物作为卡宾前体，1,5-环辛二烯氯化铱二聚体作为催化剂，其化学反应式为：
其中：
R为各种取代的苯基、噻吩基、萘基、呋喃基、环己基等基团。
2.根据权利要求1所述的α-硼代羰基化合物的合成方法，其特征在于采用如下制备步骤：
(1） 在洁净的反应器中依次加入硫叶立德、路易斯碱硼烷加成物、催化剂、添加剂和溶剂，于60℃搅拌；
（2）反应结束后，湿法过柱，残留物采用硅胶柱层析分离纯化即得到产品。
3.根据权利要求2所述的制备方法，其特征在于步骤（1）中的添加剂为氰化亚铜、醋酸铜、氟化铜、醋酸银、氯化锌、醋酸铑、氯化亚铜、三氯化铁、溴化铜、双三氟甲烷磺酸锌、双三氟甲烷磺酸铜、氯化铜中的一种或一种以上。
4.根据权利要求2中所述的制备方法，其特征在于步骤（1）中的溶剂为1,2-二氯乙烷、氯苯、二氯甲烷、氯仿、1,4-二氧六环、乙腈中的一种或一种以上。
5.根据权利要求2中所述的制备方法，其特征在于步骤（1）中的硫叶立德类化合物:路易斯碱硼烷加成物:催化剂:添加剂的摩尔比为1:（2.0~4.0）:（0.025~0.2）:（0.05~2.0）。
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