CN112759616B - 三碟烯卡宾钯化合物及其应用 - Google Patents
三碟烯卡宾钯化合物及其应用 Download PDFInfo
- Publication number
- CN112759616B CN112759616B CN202011506921.7A CN202011506921A CN112759616B CN 112759616 B CN112759616 B CN 112759616B CN 202011506921 A CN202011506921 A CN 202011506921A CN 112759616 B CN112759616 B CN 112759616B
- Authority
- CN
- China
- Prior art keywords
- compound
- cat
- catalyst
- tri
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 carbene palladium compound Chemical class 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- 229910052763 palladium Inorganic materials 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 85
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000002386 leaching Methods 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
- 238000000638 solvent extraction Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 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
- 125000002346 iodo group Chemical group I* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006411 Negishi coupling reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 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
- 229940087305 limonene Drugs 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
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 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
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- 125000004938 5-pyridyl group Chemical group N1=CC=CC(=C1)* 0.000 description 1
- 238000007341 Heck reaction Methods 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
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 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
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4238—Negishi-type, i.e. RY + R'ZnZ, in which R, R' is optionally substituted alkyl, alkenyl, alkynyl, aryl, Y is the leaving group and Z is halide or R'
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4255—Stille-type, i.e. RY + R'3SnR'', in which R is alkenyl, aryl, R' is alkyl and R'' is alkenyl or aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种三碟烯卡宾钯化合物及其应用,其结构式为式I或式II,
Description
技术领域
本发明属于有机合成技术领域,涉及一种三碟烯卡宾钯化合物及包含该化合物的催化剂在有机合成上的应用。
背景技术
金属钯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,使得金属钯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。
尽管金属钯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、底物适用范围广的金属钯催化剂及该化合物的应用,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钯催化反应,有较高的推广应用价值。
本发明是通过以下技术方案实现的:
一种三碟烯卡宾钯化合物,其结构如式I或式II所示;
在所述式I或式II中,RA相同或不同,各自独立的表示为R1-(Z1-A1-Z2)x-;
RB相同或不同,各自独立的表示为R2-(Z3-A2-Z4)y-;
RC相同或不同,各自独立的表示为R3-(Z5-A3-Z6)z-;
其中,R1、R2或R3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、Z3、Z4、Z5、Z6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;
A1、A2、A3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;
x、y和z各自独立的表示0-3的整数;
X表示F、Cl、Br、I原子、氰基、六氟磷酸基、四氟硼酸基;
Y表示N、C原子。
优选的,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,A1相同或不同,Z2相同或不同;结构单元Z3-A2-Z4中,Z3相同或不同,A2相同或不同,Z4相同或不同;结构单元Z5-A3-Z6中,Z5相同或不同,A3相同或不同,Z6相同或不同。
上述任一项的三碟烯卡宾钯化合物,在催化剂中的应用。
本发明的有益效果是:
本技术方案提供的三碟烯卡宾钯化合物用于催化剂,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,对于各类金属钯催化的反应均有较好的催化效果。而且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作进一步的阐述,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。
本技术方案中的制备方法如无特别说明均为常规方法,原材料如无特别说明均能从公开商业途径获得。
本申请的三碟烯卡宾钯化合物式I和三碟烯卡宾钯化合物式II的制备方法均为现有技术,具体的三碟烯卡宾钯化合物式I的制备方法为:
步骤1、三碟烯卡宾钯化合物式I中间体的合成:
其中X为F、Cl、Br、I原子、氰基、六氟磷酸基或四氟硼酸基中的一种;步骤2、由三碟烯卡宾钯化合物式I中间体合成三碟烯卡宾钯化合物式I:
具体的三碟烯卡宾钯化合物式II的制备方法为:
步骤1、三碟烯卡宾钯化合物式II中间体的合成:
其中X为F、Cl、Br、I原子、氰基、六氟磷酸基或四氟硼酸基中的一种;
步骤2、由三碟烯卡宾钯化合物式II中间体合成三碟烯卡宾钯化合物式II:
上述本申请提供的式I和式II所示化合物包括但不局限于Suzuki反应、Buchwald-Hartwig反应、Heck反应、Still反应、Negishi反应等的应用也属于本发明的保护范围。
实施例1化合物Cat-001的制备
首先利用原料化合物Cat001a制备Cat-001中间体(Cat-001b),再由该中间体制备化合物Cat-001,具体见以下所示:
步骤1化合物Cat-001b(化合物Cat-001中间体)的合成
向100mL两口瓶内,加入100mg(0.27mmol)Cat-001a,67mg(0.27mmol)Li2PdCl4,22mg(0.27mmol)NaOAc,15mL甲醇,室温反应2h,抽干溶剂,氧化铝柱层析,甲醇淋洗得到黄色固体86mg,收率62%。
步骤2化合物Cat-001的合成
向100mL两口瓶内,加入82mg(0.08mmol)化合物Cat-001b,64mg(0.24mmol)PPh3和15mL二氯甲烷,室温反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到淡黄色固体122mg,产率98%。
实施例2化合物Cat-002的制备
首先利用原料化合物Cat002a制备Cat-002中间体(Cat-002b),再由该中间体制备化合物Cat-002,具体见以下所示:
步骤1化合物Cat-002b的合成
向100mL两口瓶内,加入140mg(0.27mmol)的化合物Cat-002a,119mg(0.27mmol)Li2PdCl4,22mg(0.27mmol)NaOAc,15mL甲醇,室温反应2h,抽干溶剂,氧化铝柱层析,甲醇淋洗得到黄色固体135mg,收率76%。
步骤2化合物Cat-002的合成
向100mL两口瓶内,加入106mg(0.08mmol)化合物Cat-002b,77mg(0.24mmol)PC-174c和15mL二氯甲烷,室温反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到淡黄色固体154mg,产率98%。
实施例3化合物Cat-003的制备
首先利用原料化合物Cat003a制备Cat-003中间体(Cat-003b),再由该中间体制备化合物Cat-003,具体见以下所示:
步骤1化合物Cat-003b的合成
向100mL两口瓶内,加入201mg(0.27mmol)的化合物Cat-003a,170mg(0.27mmol)Li2PdI4,22mg(0.27mmol)NaOAc,15mL甲醇,室温反应2h,抽干溶剂,氧化铝柱层析,甲醇淋洗得到黄色固体184mg,收率70%。
步骤2化合物Cat-003的合成
向100mL两口瓶内,加入156mg(0.08mmol)化合物Cat-003b,67mg(0.24mmol)PCy3和15mL二氯甲烷,室温反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到淡黄色固体164mg,产率96%。
实施例4化合物Cat-004的制备
首先利用原料化合物Cat004a制备Cat-004中间体(化合物Cat-004b),再由该化合物Cat-004b制备化合物Cat-004c,由化合物Cat-004c制备化合物Cat-004,具体见以下所示:
步骤1化合物Cat-004b的合成
向100mL两口瓶内,加入125mg(0.27mmol)的化合物Cat-004a,119mg(0.27mmol)Li2PdCl4,22mg(0.27mmol)NaOAc,15mL甲醇,室温反应2h,抽干溶剂,氧化铝柱层析,甲醇淋洗得到黄色固体90mg,收率55%。
步骤2化合物Cat-004c的合成
向100mL两口瓶内,加入97mg(0.08mmol)化合物Cat-004b,64mg(0.24mmol)PPh3和15mL二氯甲烷,室温反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到淡黄色固体196mg,产率94%。
步骤3化合物Cat-004的合成
向100mL两口瓶内,加入43mg(0.05mmol)化合物Cat-004c,34mg(0.20mmol)NaPF6和15mL二氯甲烷,室温反应2h,抽干溶剂,氧化铝柱层析,二氯甲烷淋洗得到淡黄色固体54mg,产率100%。
Suzuki偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.5mmol苯硼酸、1.1mmol的叔丁醇钾和0.01%mmol的Pd催化剂,Pd催化剂分别为化合物Cat-001、化合物Cat-002、化合物Cat-003、化合物Cat-004及化合物1,然后加入1.0mmol的对甲氧基溴苯、1mL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、化合物Cat-002、化合物Cat-003、化合物Cat-004为本申请实施例1至实施例4合成化合物,化合物1为Pd(PPh3)2Cl2,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
由上可知,本发明专利方法制得的金属催化剂实施例1至4(试验编号1至4)和对比例1(试验编号5)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的零价钯中间体,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1所不能达到的。
Hartwig-Buchwald偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.1mmol的叔丁醇钾和0.01%mmol的Pd催化剂,Pd催化剂分别为化合物Cat-001、化合物Cat-002、化合物Cat-003、化合物Cat-004及化合物2,然后加入1.2mmol的二苯胺、1mL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、化合物Cat-002、化合物Cat-003、化合物Cat-004为本申请实施例1至实施例4合成化合物,化合物2为Pd(PPh3)4,反应通式如下:
其反应结果如下表2所示:
表2、催化剂用量试验结果
由上可知,本发明专利方法制得的金属催化剂实施例1至4(对应试验编号6至9)和对比例2(试验编号10)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的零价钯中间体,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。
Heck偶联反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对溴苯甲酸、1.2mmol的碳酸钾和0.01%mmol的Pd催化剂,Pd催化剂分别为化合物Cat-001、化合物Cat-002、化合物Cat-003、化合物Cat-004及化合物3,然后加入1.2mmol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、化合物Cat-002、化合物Cat-003、化合物Cat-004为本申请实施例1至实施例4合成化合物,化合物3为Pd(OAc)2,反应通式如下:
其反应结果如下表3所示:
表3、催化剂用量试验结果
/>
由上可知,本发明专利方法制得的金属催化剂实施例1至4(试验编号11至14)和对比例3(试验编号15)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的零价钯中间体,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。
Still反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.2mmol的氟化钾和0.01%mmol的Pd催化剂,Pd催化剂分别为化合物Cat-001、化合物Cat-002、化合物Cat-003、化合物Cat-004及化合物4,然后加入1.2mmol的三丁基苯基烯、1mL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、化合物Cat-002、化合物Cat-003及化合物Cat-004为专利合成化合物,化合物4为Pd2(dba)3,反应通式如下:
其反应结果如下表4所示:
表4、催化剂用量试验结果
由上可知,本发明专利方法制得的金属催化剂实施例1至4(试验编号16至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零价钯中间体,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。
Negishi反应催化比较
在装有磁子的Schlenk管中依次加入1.0mmol对甲氧基溴苯、1.2mmol的碳酸钾和0.01%mmol的Pd催化剂,Pd催化剂分别为化合物Cat-001、化合物Cat-002、化合物Cat-003、化合物Cat-004及化合物5,然后加入1.2mmol的苯基氯化锌、1mL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、化合物Cat-002、化合物Cat-003及化合物Cat-004为专利合成化合物,化合物5为Pd(dppf)Cl2,反应通式如下:
其反应结果如下表5所示:
表5、催化剂用量试验结果
由上可知,本发明专利方法制得的金属催化剂实施例1至4(试验编号21至24)和对比例5(试验编号25)相比,由于含有三碟烯大位阻基团能够稳定催化循环中的零价钯中间体,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环金属钯催化剂与常规的金属钯催化剂相比,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钯催化的反应。合成方法简便,收率较高,有较高的推广应用价值,这是常规的金属钯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,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 (2)
1.一种三碟烯卡宾钯化合物,其特征在于,其结构为:
、/>、
或 />。
2.一种三碟烯卡宾钯化合物的应用,其特征在于,上述权利要求1中的三碟烯卡宾钯化合物应用于催化剂中。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011506921.7A CN112759616B (zh) | 2020-12-18 | 2020-12-18 | 三碟烯卡宾钯化合物及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011506921.7A CN112759616B (zh) | 2020-12-18 | 2020-12-18 | 三碟烯卡宾钯化合物及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112759616A CN112759616A (zh) | 2021-05-07 |
CN112759616B true CN112759616B (zh) | 2023-07-21 |
Family
ID=75694451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011506921.7A Active CN112759616B (zh) | 2020-12-18 | 2020-12-18 | 三碟烯卡宾钯化合物及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112759616B (zh) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003013723A1 (en) * | 2001-08-10 | 2003-02-20 | Ciba Speciality Chemicals Holding Inc. | Palladium catalysts |
WO2011127579A1 (en) * | 2010-04-14 | 2011-10-20 | Kanata Chemical Technologies Inc. | Cationic palladium complexes comprising diamino carbene ligands and their use in catalysis |
-
2020
- 2020-12-18 CN CN202011506921.7A patent/CN112759616B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN112759616A (zh) | 2021-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shen et al. | The synthesis of a novel non-C2 symmetric H4-BINOL ligand and its application to titanium-catalyzed enantioselective addition of diethylzinc to aldehydes | |
CN111961087B (zh) | 含邻位碳硼烷基苯并噻唑的半夹心钌配合物及制备与应用 | |
CN110818545A (zh) | 一种酮芳基化制备取代芳基酮的方法 | |
CN114436949A (zh) | 一种四齿配体及金属络合物及其制备方法和应用 | |
CN112979714B (zh) | 一种三碟烯卡宾三齿金属配合物及其应用 | |
CN112759616B (zh) | 三碟烯卡宾钯化合物及其应用 | |
CN112940047B (zh) | 一种三碟烯卡宾钯吡啶配合物及其应用 | |
Chu et al. | Palladium (II)-Catalyzed ortho Arylation of 2-Phenylpyridines with Potassium Aryltrifluoroborates by CH Functionalization | |
JP6054386B2 (ja) | パラジウム(I)トリ−t−ブチルホスフィンブロミド二量体の製造方法および異性化反応においてそれを使用するプロセス | |
CN112876515B (zh) | 一种三蝶烯卡宾烯丙基钯化合物及其应用 | |
CN109369515B (zh) | 一种不饱和双键取代的碳环衍生物的合成方法 | |
WO2017193288A1 (en) | Synthesis of phosphine ligands bearing tunable linkage: methods of their use in catalysis | |
CN112390831B (zh) | 三碟烯环金属钯化合物及用途 | |
CN114891046B (zh) | 一种三碟烯茂金属催化剂及其应用 | |
CN111087343A (zh) | 一种羟基吡啶配体及其制备方法和催化应用 | |
CN110627831A (zh) | 二联芳缩醛膦、它们的制备方法及在偶联反应中的用途 | |
CN117551139A (zh) | 一种含有三蝶烯三齿结构的金属钯化合物及其应用 | |
CN116284156A (zh) | 一种咔唑取代的三碟烯茂金属化合物及其应用 | |
CN112047885B (zh) | 一种γ-(9-吖啶)重氮乙酰乙酸酯、γ-(9-吖啶亚甲基)-β-酮酯及其制备方法 | |
CN116789710A (zh) | 一种含有三碟烯卡宾结构的金属化合物及其应用 | |
CN116589506A (zh) | 一种三碟烯茂金属化合物及其应用 | |
CN103058803A (zh) | 一种联苯类化合物及其合成方法 | |
CN114602558B (zh) | 一种金属铱类光催化剂及其制备方法和应用 | |
CN115947765A (zh) | 一种三碟烯双桥联的茂金属化合物及其应用 | |
CN115785164A (zh) | 一种三碟烯取代的二茚铁化合物及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |