CN114891046B - 一种三碟烯茂金属催化剂及其应用 - Google Patents
一种三碟烯茂金属催化剂及其应用 Download PDFInfo
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 238000006411 Negishi coupling reaction Methods 0.000 claims description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 3
- 238000007341 Heck reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract 1
- 238000006053 organic reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 230000003197 catalytic effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 diphenyloxyphosphoryl Chemical group 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- QCAJADRKKXQEGQ-UHFFFAOYSA-J oxolane;titanium(4+);tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].C1CCOC1 QCAJADRKKXQEGQ-UHFFFAOYSA-J 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- 238000007125 Buchwald synthesis reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VFHDCDDYMMQCBF-UHFFFAOYSA-M [Cl-].[Zn+]C1=CC=CC=C1 Chemical compound [Cl-].[Zn+]C1=CC=CC=C1 VFHDCDDYMMQCBF-UHFFFAOYSA-M 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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Abstract
本发明涉及一种三碟烯茂金属催化剂及其应用,三碟烯茂金属催化剂的结构式为
Description
技术领域
本发明属于有机合成技术领域,涉及一种三碟烯茂金属催化剂及其应用。
背景技术
金属催化剂具有丰富的反应性,在有机合成中起着十分重要的作用,成为各类有机化学反应中如氢化、偶联、环加成等反应中应用最广泛的催化剂。在过去的几十年里,由于其具有反应条件温和、底物的适用范围较广、副产物无毒害以及产物易于处理等优点,使得金属催化剂被广泛地应用于实验室研究、制药业已经精细化工领域,用来合成很多种类型的有机化合物。
以Suzuki反应为例,Suzuki反应是最常用的构筑芳香环偶联反应之一,其中最为常用的就是金属钯催化剂,该类型的催化体系得到了非常广泛的研究,由于钯金属催化剂对于空气和热有着相对较高的稳定性,且在催化反应中易于回收利用,反应有着较高的活性,而且其中一些比较成熟的体系可以在比较温和的条件下催化活化和非活化氯苯的和苯硼酸的偶联,因此成为现代有机合成最重要的手段之一,被应用到很多有机分子合成领域。
尽管金属催化剂的研究已经有了很大的进展,但是其在工业上的应用仍然存在着很多的问题和缺陷。由于其价格昂贵,对于许多配体和催化剂体系而言,存在着结构复杂、制备条件苛刻、容易失活及反应后难以回收利用等问题因此高稳定性、高活性、底物适用范围广、可回收利用性、造价低廉、有很高的TON和TOF的金属催化剂依然是很重要的研究内容。
发明内容
本发明的目的在于克服现有技术的不足之处,提供一种具有高稳定性、高活性、底物适用范围广的一种三碟烯茂金属催化剂及其应用,该类化合物合成步骤简单,收率高,成本较低,适用于各类不同的金属催化反应,有较高的推广应用价值。
为实现上述目的,本发明是通过以下技术方案实现的:
一种三碟烯茂金属催化剂,其结构如式I所示,
式I
所所述式I中,R可相同或不同,各自独立的表示为R1-(Z1-A-Z2)x-;
其中,R1各自独立的选自-H、-D、-T、-Cl、-CN、-CD3、-CF3、-OCF3、碳原子数为1-15的烷基、碳原子为1-15的烷氧基、碳原子数为2-15的直链烯烃基、氟代的碳原子数为1-15的烷基、氟代的碳原子数为1-15的烷氧基或氟代的碳原子数为2-15的直链烯烃基中、9-三碟烯基的任意一种;
Z1、Z2各自独立的选自-O-、-S-、-OCO-、-COO-、-CO-、-CH2O-、-OCH2-、-OCF2-、碳原子数为1-15的直链烷基、碳原子数为2-15的直链烯烃基、碳原子数为2-15的直链炔基、氟代的碳原子数为1-15的直链烷基、氟代的碳原子数为2-15的烯烃基或碳碳单键中的至少一种或为无;
A各自独立的选自1,4-亚环己基、1,4-亚苯基、二苯基氧磷基、N-苯基-咔唑-2-基、N-苯基-咔唑-3-基、9,10-蒽基、1-萘基、2-萘基、4-三苯胺基、2,5-嘧啶基、3,9-咔唑基、2,5-吡啶基、2,5-四氢-2H-吡喃基、1,3-二噁烷-2,5-基、1,2,4-噁二唑-3,5-基、氟代的1,4-亚环己基、氟代的吡喃环二基、环内酯二基、五元氧杂环二基、五元硫杂环二基、五元氮杂环二基或碳碳单键中的一种或为无;
x和y各自独立的表示0-3的整数;
X表示Cl、Br、I原子;
M表示Ti、Zr、Hf。
进一步的,所述x或y均为2或3时,结构单元Z1-A1-Z2中,Z1相同或不同,A相同或不同,Z2相同或不同。
上述任一项的三碟烯茂金属催化剂应用于催化剂中。
进一步的,所述催化剂应用于包括但不限于Suzuki反应、Buchwald-Hartwig反应、Heck反应、Still反应或Negishi反应中。
本发明的有益效果是:
本专利提供的三碟烯茂金属催化剂,制备简便,收率高,适用于多种底物,催化剂使用量可降至万分之一,对于各类金属催化的反应均有较好的催化效果。对于研究催化反应的进展与应用,具有重要的应用价值。
具体实施方式
以下结合具体实施例对本发明的技术方案进行详细的说明,以下的实施例仅是示例性的,仅能用来解释和说明本发明的技术方案,而不能解释为是对本发明技术方案的限制。
实施例1 化合物Cat-001的制备:
向500 mL两口瓶内,加入318mg (1.0 mmol) Cat-001a,100mL的四氢呋喃,液氮/丙酮冷却至-78℃,缓慢滴加0.6mL(2.0mol/L)的丁基锂的己烷溶液,滴加完成后保持30分钟,然后加入166mg(0.5 mmol)四氯化钛四氢呋喃配合物,保持温度反应2小时,缓慢升至室温,加入20mL的乙酸乙酯和水,萃取三次,合并有机相,抽干溶剂。抽干溶剂,氧化铝柱层析,二氯甲烷:甲醇=10:1淋洗得到红色固体372mg,收率94%。
实施例2 化合物Cat-002的制备:
向500 mL两口瓶内,加入475mg (1.0 mmol) Cat-002a,100mL的四氢呋喃,液氮/丙酮冷却至-78℃,缓慢滴加0.6mL(2.0mol/L)的丁基锂的己烷溶液,滴加完成后保持30分钟,然后加入166mg(0.5 mmol)四溴化锆四氢呋喃配合物,保持温度反应2小时,缓慢升至室温,加入20mL的乙酸乙酯和水,萃取三次,合并有机相,抽干溶剂。抽干溶剂,氧化铝柱层析,二氯甲烷:甲醇=10:1淋洗得到红色固体547mg,收率89%。
实施例3 化合物Cat-003的合成 :
向500 mL两口瓶内,加入507mg (1.0 mmol) Cat-003a,100mL的四氢呋喃,液氮/丙酮冷却至-78℃,缓慢滴加0.6mL(2.0mol/L)的丁基锂的己烷溶液,滴加完成后保持30分钟,然后加入166mg(0.5 mmol)四氯化钛四氢呋喃配合物,保持温度反应2小时,缓慢升至室温,加入20mL的乙酸乙酯和水,萃取三次,合并有机相,抽干溶剂。抽干溶剂,氧化铝柱层析,二氯甲烷:甲醇=10:1淋洗得到红色固体522mg,收率90%。
实施例4 Suzuki偶联反应催化比较:
在装有磁子的Schlenk管中依次加入1.5 mmol苯硼酸、1.1 mmol的叔丁醇钾和0.01%mmol的催化剂(化合物Cat-001、Cat-002、Cat-003、1),然后加入1.0 mmol的对甲氧基溴苯、1 mL异丙醇,80℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=2:1),得到无色的产品,称重后计算产率。
其中化合物Cat-001、Cat-002、Cat-003为实施例1至3合成的化合物,化合物1为商用对比催化剂,反应通式如下:
其反应结果如下表1所示:
表1、Suzuki反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
1 | Cat-001 | 88 |
2 | Cat-002 | 95 |
3 | Cat-003 | 92 |
4 | 1 | 67 |
由上可知,本发明专利方法制得的三碟烯茂金属催化剂(实施例1-3,试验编号1-3)在应用中和对比例1(实验编号4)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的中间体,使得催化效率提升,在仅用万分之一的用量就能以非常高的收率实现Suzuki催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例6 Hartwig-Buchwald偶联反应催化比较:
在装有磁子的Schlenk管中依次加入1.0 mmol对甲氧基溴苯、1.1 mmol的叔丁醇钾和0.01%mmol的催化剂(化合物Cat-001、Cat-002、Cat-003、2),然后加入1.2 mmol的二苯胺、1 mL甲苯,100℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=2:1),得到无色的产品,称重后计算产率。
其中化合物Cat-001、Cat-002、Cat-003为专利合成化合物,化合物2为商用对比催化剂,反应通式如下:
其反应结果如下表2所示:
表2、Hartwig-Buchwald反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
5 | Cat-001 | 88 |
6 | Cat-002 | 91 |
7 | Cat-003 | 85 |
8 | 2 | 54 |
由上可知,与实施例5类似,本发明专利方法制得的三碟烯茂金属催化剂(实施例1-3,实验编号5-7)在应用中和对比例2(实验编号8)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的中间体,使得催化效率提升,在仅用万分之一的用量就能以非常高的收率实现Hartwig-Buchwald催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例7 Heck偶联反应催化比较:
在装有磁子的Schlenk管中依次加入1.0 mmol对溴苯甲酸、1.2 mmol的碳酸钾和0.01%mmol的催化剂(化合物Cat-001、Cat-002、Cat-003、3),然后加入1.2 mmol的丙烯酸、1mL二甲苯,120℃下搅拌2h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4:1),得到无色的产品,称重后计算产率。
其中化合物Cat-001、Cat-002、Cat-003为专利合成化合物,化合物3为商用对比催化剂,反应通式如下:
其反应结果如下表3所示:
表3、Heck反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
9 | Cat-001 | 84 |
10 | Cat-002 | 91 |
11 | Cat-003 | 85 |
12 | 3 | 61 |
由上可知,与实施例5类似,本发明专利方法制得的三碟烯茂金属催化剂(实施例1-3,试验编号9-11)和对比例3(试验编号12)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的中间体,使得催化效率提升,在仅用万分之一的用量就能以非常高的收率实现Heck偶联催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例8 Still反应催化比较:
在装有磁子的Schlenk管中依次加入1.0 mmol对甲氧基溴苯、1.2 mmol的氟化钾和0.01%mmol的催化剂(化合物Cat-001、Cat-002、Cat-003、4),然后加入1.2 mmol的三丁基苯基烯、1 mL二氧六环,100℃下搅拌6h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4:1),得到无色的产品,称重后计算产率。
其中化合物Cat-001、Cat-002、Cat-003为专利合成化合物,化合物4为商用对比催化剂,反应通式如下:
其反应结果如下表4所示:
表4、Still反应对比试验结果
试验编号 | 采用催化剂 | 收率 |
13 | Cat-001 | 81 |
14 | Cat-002 | 82 |
15 | Cat-003 | 86 |
16 | 4 | 43 |
由上可知,与实施例5类似,本发明专利方法制得的三碟烯茂金属催化剂(实施例1-3,试验编号13-15)和对比例4(试验编号16)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的中间体,使得催化效率提升,在仅用万分之一的用量就能以非常高的收率实现Still催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
实施例9 Negishi反应催化比较:
在装有磁子的Schlenk管中依次加入1.0 mmol对甲氧基溴苯、1.2 mmol的碳酸钾和0.01%mmol的催化剂(化合物Cat-001、Cat-002、Cat-003、5),然后加入1.2 mmol的苯基氯化锌、1 mL四氢呋喃,60℃下搅拌6h。然后用二氯甲烷溶解后拌入氧化铝,柱层析(淋洗液二氯甲烷/石油醚=4:1),得到无色的产品,称重后计算产率。
其中化合物Cat-001、Cat-002、Cat-003为专利合成化合物,化合物5为商用对比催化剂,反应通式如下:
其反应结果如下表5所示:
表5、Negishi反应对比试验结果
试验编号 | 采用催化剂 | 收率(%) |
17 | Cat-001 | 92 |
18 | Cat-002 | 90 |
19 | Cat-003 | 88 |
20 | 5 | 43 |
由上可知,与实施例5类似,本发明专利方法制得的三碟烯茂金属催化剂(实施例1-3,试验编号17-19)和对比例4(试验编号20)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的中间体,使得催化效率提升,在仅用万分之一的用量就能以非常高的收率实现Negishi催化反应,而在工业生产中,催化剂的用量对于原材料的成本控制,后处理的难易程度均存在非常大的影响,在成本控制上有着巨大的优势,这是对比例所不能达到的。
综上可知,本发明专利所制得的三碟烯茂金属催化剂与常规的催化剂相比,有着更好的催化效果,对于各种不同取代基的反应底物也有着很好的普遍适用性,在催化剂用量上也有着显著的优势,仅需万分之一的用量就可以保证催化反映的进行,能普遍适用于各类金属催化的反应。合成方法简便,收率较高,有较高的推广应用价值,这是常规的金属催化剂所不能实现的,这样的效果是本领域技术人员所不能预料到的。
尽管结合优选实施例对本发明进行了说明,但本发明并不局限于上述实施例和附图,应当理解,在本发明构思的引导下,本领域技术人员可进行各种修改和改进,所附权利要求概括了本发明的范围。
Claims (3)
1.一种三碟烯茂金属催化剂,其特征在于,其结构式为
2.一种三碟烯茂金属催化剂的应用,其特征在于,上述权利要求1中的三碟烯茂金属催化剂应用于催化剂中。
3.根据权利要求2所述的三碟烯茂金属催化剂的应用,其特征在于,所述催化剂应用于Suzuki反应、Buchwald-Hartwig反应、Heck反应、Still反应或Negishi反应中。
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