CN112028762A - 钌催化的环丙醇与硫叶立德的烷基化反应用于合成1,5-二酮化合物 - Google Patents
钌催化的环丙醇与硫叶立德的烷基化反应用于合成1,5-二酮化合物 Download PDFInfo
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- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 title claims description 12
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- 238000000034 method Methods 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
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- 238000010898 silica gel chromatography Methods 0.000 claims description 9
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- PYPUDRHWKONOEB-UHFFFAOYSA-K 1-methyl-4-propan-2-ylbenzene;ruthenium(1+);ruthenium(2+);trichloride Chemical compound [Ru]Cl.Cl[Ru]Cl.CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 PYPUDRHWKONOEB-UHFFFAOYSA-K 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- -1 cyclopropanol compound Chemical class 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 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 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
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- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
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- UCXDWSTYBSBFFB-UHFFFAOYSA-L 1-methyl-4-propan-2-ylbenzene;ruthenium(2+);dichloride Chemical compound Cl[Ru]Cl.CC(C)C1=CC=C(C)C=C1 UCXDWSTYBSBFFB-UHFFFAOYSA-L 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
本发明涉及一种钌催化的环丙醇与硫叶立德的烷基化反应,通过该方法可以合成得到一系列1,5‑二酮化合物。该方法通过钌催化环丙醇发生β‑碳消除开环,并采用安全、稳定,且容易制备的硫叶立德作为卡宾前体,因此在构建1,5‑二酮领域具有良好的适用性。
Description
技术领域
涉及一种钌催化的环丙醇与硫叶立德的烷基化反应构建1,5-二酮的合成新方法,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C-H活化反应1和C-C活化反应2因此能够以步骤经济和原子经济的方式合成有机化合物而得到了长足的进展。与C-H键活化相比,由于C-C键的高度惰性,尽管它提供了一种更直接的重建分子骨架的途径,但C-C激活仍然具有挑战性和局限性3。而C-C氧化加成2h和β-碳消除4,5一直是实现C-C裂解的最重要和最通用的方法。特别是张力环的β-碳消除已经成功应用于C-C活化邻域,因为环张力的释放使得惰性的C-C键更容易断裂5。近年来,环丙醇作为一种容易获得的小环构建单元,在有机合成中受到了广泛的关注。通过过渡金属催化的自由基开环或β-碳消除的方法,发展了各种各样的β位官能团化的酮的合成方法,如烷基化、芳基化、烯基化、烷基化、氰化、羰基化和卤化等6。
另一方面,自20世纪初首次被发现以来,能够进行多种反应的金属卡宾化合物已成为重要的中间体7。王剑波课题组和Murakami课题组分别报道了张力环与重氮化合物或者腙类化合物的卡宾插入反应,该反应通过β-碳消除实现C-C键的断裂8。基于我们一直以来对于硫叶立德的研究,我们这里报道了一种环丙醇与硫叶立德的烷基化反应,该反应涉及依次进行的β-碳消除开环和卡宾转移反应。该方法提供了一种有效而实用的合成1,5-二酮化合物的新方法。
发明内容
针对现存的通过卡宾偶联反应构建1,5-二酮化合物的方法存在的底物适用性等方面的问题,本发明的目的是为了提供一种钌催化的环丙醇与硫叶立德的烷基化反应用于合成1,5-二酮化合物,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环丙醇为起始原料,其化学反应式如下所示:
其中:
R为各种取代的苯基、各种取代的苄基、环戊基、环己基、环庚基、碳原子数为2~7的直链烷烃等基团;
R’为各种取代的苯基、呋喃基、1-萘基、2-萘基等基团;
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、环丙醇、催化剂和溶剂,放入80℃油浴中反应30h;
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。
其特征在催化剂为对甲基异丙基苯二氯化钌(II)二聚体、碘化亚铜中的一种;
溶剂为甲苯、三氟乙醇、乙腈、四氢呋喃、1,2-二氯乙烷、甲醇的一种。步骤(1)中环丙醇化合物:硫叶立德化合物:催化剂的摩尔比为(2.0-5.0):1:(0.025-0.1)。
本发明采取以上技术方案,其具有以下优点:相比于传统的合成1,5-二酮化合物的方法的底物适用性的问题,本发明原料稳定且易得,是一种温和的替代传统的合成1,5-二酮化合物的方法,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化合物的结构。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硫叶立德(19.6 mg,0.1 mmol)、苄基环丙醇(44.5 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(3.1 mg, 0.005 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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淡黄色固体,熔点范围为65.1-66.7 °C,收率为90%。1H NMR (400 MHz, Chloroform-d) δ 7.91 (d, J= 7.7 Hz, 2H), 7.55 (t, J = 7.3 Hz, 1H), 7.44 (t, J = 7.5 Hz, 2H), 7.31 (t, J= 7.3 Hz, 2H), 7.26 – 7.16 (m, 3H), 3.69 (s, 2H), 2.94 (t, J = 7.0 Hz, 2H),2.59 (t, J = 6.9 Hz, 2H), 1.99 (p, J = 7.0 Hz, 2H); 13C NMR (101 MHz,Chloroform-d) δ 208.15, 199.85, 136.88, 134.25, 133.18, 129.52, 128.87,128.70, 128.16, 127.16, 50.33, 40.97, 37.45, 18.29. HRMS (ESI): m/z计算值C18H18NaO2 +: 289.1199,实测值: 289.1195。
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硫叶立德(21 mg,0.1 mmol)、苄基环丙醇(44.5 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(1.6 mg, 0.025 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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淡黄色液体收率为65%。1H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.67 (m, 2H), 7.38 – 7.28(m, 4H), 7.25 – 7.16 (m, 3H), 3.69 (s, 2H), 2.93 (t, J = 7.0 Hz, 2H), 2.59(t, J = 7.0 Hz, 2H), 2.40 (s, 3H), 1.98 (p, J = 7.0 Hz, 2H); 13C NMR (151 MHz,Chloroform-d) δ 208.14, 200.05, 138.46, 136.95, 134.28, 133.92, 129.53,128.86, 128.67, 128.57, 127.15, 125.38, 50.32, 41.01, 37.50, 21.46, 18.34.HRMS (ESI): m/z计算值C19H20NaO2 +: 303.1356,实测值: 303.1353。
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硫叶立德(22.6 mg,0.1 mmol)、苄基环丙醇(44.5 mg,0.3 mmol)、碘化亚铜(1 mg, 0.05 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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淡黄色固体,熔点范围为78.3-80.5 °C收率为45%。1HNMR (400 MHz, Chloroform-d) δ 7.90 (d, J =8.9 Hz, 2H), 7.31 (t, J = 7.2 Hz, 2H), 7.25-7.18 (m, 3H), 6.91 (d, J = 8.9Hz, 2H), 3.86 (s, 3H), 3.69 (s, 2H), 2.89 (t, J = 7.1 Hz, 2H), 2.59 (t, J =6.9 Hz, 2H), 1.98 (p, J = 7.0 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) δ208.18, 198.42, 163.53, 134.26, 130.42, 129.98, 129.51, 128.83, 127.11,113.79, 55.56, 50.28, 41.07, 37.11, 18.53. HRMS (ESI): m/z计算值C19H20NaO3 +:319.1305,实测值: 319.1300。
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硫叶立德(19.6 mg,0.1 mmol)、苯基环丙醇(40.3 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(3.1 mg, 0.05 mmol)、甲醇(2 ml),置于80℃油浴中搅拌30h。
(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白色固体,熔点范围为55.7-57.4 °C收率为45%。1H NMR (400 MHz, Chloroform-d) δ 7.98 (d, J =7.2 Hz, 4H), 7.55 (t, J = 7.4 Hz, 2H), 7.48 – 7.33 (m, 4H), 3.12 (t, J = 6.9Hz, 4H), 2.20 (p, J = 7.0 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) δ 200.01,136.95, 133.20, 128.72, 128.19, 37.71, 18.82. HRMS (ESI): m/z计算值C17H16NaO2 +:275.1043,实测值: 275.1045。
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硫叶立德(19.6 mg,0.1 mmol)、环己基环丙醇(42.1 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(3.1 mg, 0.05 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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淡黄色液体收率为96%。1H NMR (400 MHz, Chloroform-d) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t,J = 7.4 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 3.00 (t, J = 7.0 Hz, 2H), 2.57 (t,J = 6.9 Hz, 2H), 2.38 – 2.28 (m, 1H), 2.00 (p, J = 7.0 Hz, 2H), 1.90 – 1.57(m, 6H), 1.39 – 1.25 (m, 4H); 13C NMR (101 MHz, Chloroform-d) δ 213.97,200.08, 136.93, 133.16, 128.70, 128.17, 50.93, 39.56, 37.68, 28.60, 25.94,25.76, 18.38. HRMS (ESI): m/z计算值C17H22NaO2 +: 281.1512,实测值: 281.1515。
实施案例6:化合物6的合成
(1) 氩气条件下,在洁净的反应器中依次加入硫叶立德(24.6 mg,0.1 mmol)、苄基环丙醇(44.5 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(3.1 mg, 0.05 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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淡黄色固体,熔点90.2-92.4 °C,收率为81%。1H NMR (400 MHz, Chloroform-d) δ 8.42 (s, 1H), 7.97(dd, J = 15.9, 8.2 Hz, 2H), 7.87 (d, J = 8.8 Hz, 2H), 7.57 (dt, J = 19.1, 7.3Hz, 2H), 7.30 (t, J = 7.0 Hz, 2H), 7.23 (dd, J = 15.9, 5.2 Hz, 3H), 3.71 (d,J = 2.1 Hz, 2H), 3.07 (td, J = 7.0, 2.0 Hz, 2H), 2.63 (td, J = 6.9, 2.0 Hz,2H), 2.05 (pd, J = 7.0, 2.0 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) δ 208.21,199.79, 135.68, 134.24, 134.20, 132.62, 129.86, 129.69, 129.53, 128.87,128.55, 128.53, 127.87, 127.16, 126.87, 123.90, 50.36, 41.00, 37.49, 18.43;HRMS (ESI): m/z计算值C22H20NaO2 +: 339.1356,实测值: 339.1354。
实施案例7:化合物7的合成
(1) 氩气条件下,在洁净的反应器中依次加入硫叶立德(19.6 mg,0.1 mmol)、正戊基环丙醇(38.5 mg,0.3 mmol)、对甲基异丙基苯二氯化钌(II)二聚体(3.1 mg, 0.05 mmol)、三氟乙醇(2 ml),置于80℃油浴中搅拌30h。
(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白色固体,熔点范围为53.7-55.4 °C,收率为93%。1H NMR (400 MHz, Chloroform-d) δ 7.99 – 7.93(m, 2H), 7.59 – 7.52 (m, 1H), 7.46 (t, J = 7.5 Hz, 2H), 3.01 (t, J = 7.0 Hz,2H), 2.54 (t, J = 7.0 Hz, 2H), 2.40 (t, J = 7.5 Hz, 2H), 2.02 (p, J = 7.0 Hz,2H), 1.57 (p, J = 7.5 Hz, 2H), 1.35 – 1.22 (m, 4H), 0.88 (t, J = 7.0 Hz, 3H);13C NMR (101 MHz, Chloroform-d) δ 211.00, 199.94, 137.02, 133.16, 128.72,128.18, 42.97, 41.72, 37.65, 31.55, 23.69, 22.55, 18.48, 14.00; HRMS (ESI):m/z计算值C16H22NaO2 +: 269.1512,实测值: 269.1515。
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Claims (5)
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、环丙醇、催化剂和溶剂,放入80℃油浴中反应30h;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,其特征在催化剂为对甲基异丙基苯二氯化钌(II)二聚体、碘化亚铜中的一种。
4.根据权利要求2所述的制备方法,其特征在于溶剂为甲苯、三氟乙醇、乙腈、四氢呋喃、1,2-二氯乙烷、甲醇的一种。
5.根据权利要求2所述的制备方法,其特征在于环丙醇化合物:硫叶立德化合物:催化剂的摩尔比为(2.0~5.0):1:(0.025~0.1)。
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