WO2020198464A1 - Hydrogénation électrochimique hautement sélective d'alcynes - Google Patents

Hydrogénation électrochimique hautement sélective d'alcynes Download PDF

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WO2020198464A1
WO2020198464A1 PCT/US2020/024943 US2020024943W WO2020198464A1 WO 2020198464 A1 WO2020198464 A1 WO 2020198464A1 US 2020024943 W US2020024943 W US 2020024943W WO 2020198464 A1 WO2020198464 A1 WO 2020198464A1
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nmr
mhz
cathode
ppm
anode
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PCT/US2020/024943
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Haibo Ge
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The Trustees Of Indiana University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B31/00—Reduction in general
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof

Definitions

  • Cis-alkenes are important scaffolds in various natural products, pharmaceuticals, and organic functional materials. They are also key building blocks for developing molecular complexity from their stereospecific transformations. Current methods use catalytic reduction with transition metals for synthesis of cis-alkenes. However, transition metal-catalyzed selective semi-hydrogenation of alkynes to cis-olefms suffers from drawbacks including the use of stoichiometric amounts of reducing reagents, poor chemo- and stereo-selectivity and overreduction of alkenes to alkanes. A need exists for cost-effective hydrogenation methods with improved efficiency and environmental friendliness.
  • Embodiments of the invention include an electrochemical method to prepare an alkene, such as a cis-alkene, from an alkyne by reacting an alkyne in a reactor in the presence of an electrochemical cell having a cathode and an anode.
  • Embodiments of the invention further include an electrochemical method to prepare an alkane from an alkyne by reacting an alkyne in a reactor in the presence of an electrochemical cell having a cathode and an anode.
  • Embodiments of the invention also include an electrochemical method to prepare an alkane from an alkene, such as a cis-alkene, by reacting an alkene, such as a cis-alkene, in a reactor in the presence of an electrochemical cell having a cathode and an anode.
  • the alkene is not a trans-alkene.
  • R 1 , R 2 , R 3 , R 4 , R 5 , Rr, and R 7 are independently selected from H; CN; alkyl, such as methyl, ethyl, propyl, n-butyl, t-butyl, and the like; alkoxy, vinyl, alkenyl, formyl; CF 3 ; CCl 3 ; halide, C 6 H 5 ; amide such as C(0)N(CH 3 ) 2 , C(0)N(CH 2 CH 3 )2, C(0)N(CH 2 CH 2 CH 3 ) 2 , and the like; acyl, such as C(O)- C 6 3 ⁇ 4, and the like; ester, amino, thioalkoxy, phosphino, and the like; halide atom (F, Cl, Br, I), or any sulfur-containing group (e.g., triflate, sulfonate, tosylate) and the like; Arylating compound may be a heterocyclic aromatic compound
  • FIGS. 1A and IB illustrate fluorescence images of products 4a-4d in toluene (2.0 c 10 '5 M) under UV light (365 nm) and before and after grinding.
  • FIGS. 2A-2G illustrate (A-C) SEM micrographs of palladium nanoparticles formed on the cathode surface. (D) X-ray diffractograms of the palladium nanoparticles and (E-G) SEM micrographs of the Pd nanoparticles from the solution.
  • FIG. 3 illustrates hydrogenation of alkynes to Z-alkenes and construction of
  • FIG. 4 illustrates a plausible mechanism of electrochemical selective hydrogenation of alkynes.
  • FIGS. 5A-5B illustrates normalized UV-Vis absorption and emission spectra of products 4a-4d in toluene.
  • FIG. 6 illustrates emission color coordinates of product 4b in the CIE 1931 chromaticity diagram.
  • FIG. 7 illustrates fluorescence emission spectra of unground and ground products 4a-4d.
  • FIG. 8 illustrates a DSC trace of product 4b in different states.
  • FIG. 9 illustrates powder XRD patterns of product 4b in different states.
  • FIG. 10 illustrates TGA curves of product 4b.
  • FIG. 11 illustrates cyclic voltammetry of 1, 2-diphenyl ethyne.
  • FIG. 12 is a 3 ⁇ 4 and deuterium labelled NMR spectra of the identified product.
  • FIG. 13 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 14 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 15 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 16 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 17 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 18 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 19 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 20 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 21 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 22 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 23 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 24 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 25 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 26 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 27 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 28 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 29 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 30 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 31 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 32 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 33 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 34 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 35 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 36 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 37 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 38 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 39 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 40 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 41 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 42 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 43 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 44 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 45 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 46 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 47 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 48 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 49 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 50 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 51 is a 3 ⁇ 4 and/or a 13 C NMR spectra of the identified product.
  • FIG. 52 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 53 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 54 is a 'H and/or a 13 C NMR spectra of the identified product.
  • FIG. 55 is a 'H and deuterium labelled NMR spectra of the identified product.
  • FIG. 56 illustrates additional embodiments of the synthetic processes of the invention.
  • Mechanochromic fluorescent materials are a class of“smart” materials with fluorescent properties that change in response to external force stimuli.
  • Alkynes 1 were prepared according to the literature procedures (M. Takimoto, S. Usami, Z. Hou, Scandium-catalyzed regio- and stereospecific methylalumination of silyloxy/alkoxy-substituted alkynes and alkenes. J. Am. Chem. Soc. 131, 18266-18268 (2009); C. Feng, T.-R Loh, Palladium-catalyzed decarboxyl ative cross-coupling of alkynyl carboxylic acids with arylboronic acids. Chem. Commun. 46, 4779-4781 (2010); A. Sagadevan, K.
  • Ethene-l,l,2-triyltribenzene was synthesized according to the literature procedures (C.-L. Sun, Y.-F. Gu, B. Wang, Z.-J. Shi, Direct arylation of alkenes with aryl iodides/bromides through an organocatalytic radical process. Chem. Eur. J. 17, 10844-10847 (2011). 1, 1,2,2- tetraphenylethene was prepared according to the literature procedures (C. Zhou, R. C.
  • IR Infrared
  • IR Infrared
  • IR Infrared
  • XRD X-ray diffraction
  • Fluorescence spectra were obtained on an Agilent Technologies Cary Eclipse Fluorescence Spectrometer. Absorption spectra were collected on a Thormo Scientific Evolution 600
  • Cyclic voltammetry (CV) measurement was performed on CH Instruments electrochemical workstation using an Ag/AgCl reference electrode, a platinum wire counter electrode, and a platinum plate working electrode.
  • Standard XRD patterns PDF 00-001-0228 for PdCl 2 and PDF 01-087-0643 for Pd were used for identifying the peaks.
  • DSC Differential scanning calorimetry
  • TGA thermal gravimetric analyzer
  • the electrochemical hydrogenation was carried out in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode, la (0.80 mmol, 142.4 mg), Pd source (0.5 mol%), base (0.5 equiv), electrolyte (1.0 equiv) and solvent (8.0 mL) were placed in a three-necked round-bottomed flask at indicated temperature with a indicated constant current maintained for 2.5 h. The mixture was cooled to room temperature, and diluted with 20 mL of EtOAc. The organic mixture was then washed with brine, dried over anh. Na 2 S0 4 , and evaporated under vacuum.
  • Electrochemical hydrogenation was carried out in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode. 1 (0.80 mmol), PdCl 2 (0.5 mol%,
  • Electro-reduction reaction was performed in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode. 1 (0.80 mmol), PdCl 2 (0.5 mol%, 0.7 mg), Me2NH (1.0 equiv, 0.4 mL, 2.0 M in the methonal), " n B ⁇ 4NI (2.0 equiv, 591 mg) and MeCN (8.0 mL) were placed in a three-necked round-bottomed flask at 60 °C with a constant current of 0.3 A maintained for 2.5-8 h. The mixture was cooled to room temperature, and diluted with 20 mL of EtOAc.
  • Electro-reduction reaction was performed in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode. 2 (0.80 mmol), PdCl 2 (0.5 mol%, 0.7 mg), Me 2 NH (1.0 equiv, 0.4 mL, 2.0 M in the methonal), " n B ⁇ 4NI (2.0 equiv, 291 mg) and MeCN (8.0 mL) were placed in a three-necked round-bottomed flask at 60 °C with a constant current of 0.3 Amaintained for 2.5-10 h. The mixture was cooled to room temperature, and diluted with 20 mL of EtOAc.
  • the electrochemical hydrogenation was carried out in three-necked round- bottomed flask (100 mL), with a graphite rod anode and reused with the unwashed Pt electrode as cathode, la (0.80 mmol, 142.4 mg), recycled Pd nanoparticles (filtration solution), Me?NH (0.5 equiv, 0.2 mL, 2.0 M in the methonal), " n B ⁇ 4NI (1.0 equiv, 295.5 mg) and MeOH (8.0 mL) were placed in a three-necked round-bottomed flask at 60 °C with a constant current of 0.1 A maintained for 2.5 h.
  • the electrochemical hydrogenation was carried out in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode. 1,1, 2, 2-tetraphenyl ethene (0.20 mmol, 64.4 mg), PdCl 2 (2.0 mol%, 0.7 mg), Me 2 NH (1.0 equiv, 0.1 mL, 2.0 M in the methonal), "BU4NI (2.0 equiv, 147.8 mg) and MeCN (6.0 mL) were placed in a three-necked round- bottomed flask at 60 °C with a constant current of 0.3 A maintained for 10 h.
  • Electrochemical hydrogenation was carried out in three-necked round-bottomed flask (10 mL), with a graphite rod anode and a platinum disc cathode.
  • l,l,2,2-tetra(thiophen-2-yl)ethene (0.20 mmol, 71.2 mg)
  • PdCl 2 2.0 mol%, 0.7 mg
  • Me 2 NH 1.0 equiv, 0.1 mL, 2.0 M in the methonal
  • n B ⁇ 4NI 2.0 equiv, 147.8 mg
  • MeCN 6.0 mL
  • Heteroarylethynes were exclusively reduced to the corresponding Z-alkenes without affecting the heteroaromatic rings (2e and 2f). Furthermore, hydrogenation of unactivated dialkyl acetylenes also provided the corresponding Z-olefms in high yields with excellent selectivity (21-2n and 2q- 2x). Moreover, terminal alkynes can be easily hydrogenated (2o-2p). As shown in Table 1, a variety of valuable functionalities such as amino, chloro, cyano, ether, fluoro, methoxyl, methyl, silicon, trifluoromethyl, and heterocycle were all well tolerated. Benzyl and naphthalene were compatible under the present conditions (2q-2t). Table 1 shows the electrochemical selective hydrogenation of various alkynes to Z-alkenes.
  • the metal electrode is not sacrificed under the present conditions. Moreover, deuterated 1,2-diphenyl ethane was obtained with 100% of deuterium incorporation in 83% yield with CD 3 CN as the solvent under the standard reaction conditions (FIG. 12). Alkenes were also reduced cleanly to alkanes with the inventive processes. The inventive processes also showed good catalytic activity toward mono-, di-, tri-, and tetra-substituted alkenes (Table 3). Table 3 shows the electrochemical selective hydrogenation of alkenes to alkanes.
  • TPA-bearing (z)-2-(4-styrylphenyl)oxazole scaffolds were synthesized (4a-4d) (FIG. 3 and Table 4).
  • (z)-l-chloro-4-styrylbenzene and (z)-l,2-bis(4- chlorophenyl)ethane were used as starting materials.
  • Palladium-catalyzed C-H/C-Cl crosscoupling of TPA-bearing oxazoles (5) with 2g or 2j was performed to obtain the corresponding TPA-bearing (z)-2-(4-styrylphenyl)oxazole scaffolds 4a-4d (Table 4).
  • Table 4 shows the synthesis of TPA-containing (z)-2-(4-styrylphenyl)oxazoles.
  • Product 4b was further investigated and its powder phase characteristics were studied by differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) analysis.
  • DSC experiment of the unground 4b did not present endothermic or exothermic peaks.
  • the ground 4b exhibited an obvious endothermic peak, indicating a transition from a metastable state to the stable state (Fig. 8).
  • the PXRD patterns of the pristine solid of 4b exhibited sharp and intense reflections, whereas the sharp peaks disappeared after grinding (Fig. 9). These observations demonstrated a morphological transition from the crystalline to amorphous phase.
  • thermal stability was also evaluated by thermal gravimetric analyzer analysis (Fig. 10). Thermal decomposition temperatures (T d ) of 4b is 343 °C, which indicate that 4b is thermally stable.
  • the palladium catalyst is recycleable.
  • Other metal catalysts useful in the invention include rhodium, iron, cobalt, ruthenium, iridium, platinum, and copper catalysts, including but not limited to Cu(OTf)2 and CuCl 2 .

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Abstract

L'invention concerne des procédés électrochimiques de préparation d'un alcane ou d'un alcène, tel qu'un cis-alcène, à partir d'un alcyne, ou d'un alcane à partir d'un alcène. Le procédé fait appel à une cellule électrochimique comportant une cathode et une anode et à un réacteur.
PCT/US2020/024943 2019-03-26 2020-03-26 Hydrogénation électrochimique hautement sélective d'alcynes WO2020198464A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120761A (en) * 1977-12-15 1978-10-17 Monsanto Company Electrochemical process for the preparation of acetals of 2-haloaldehydes
US5035777A (en) * 1988-03-07 1991-07-30 Atochem North America, Inc. Preparation of alkanesulfonyl halides and alkanesulfonic acids
US20040206633A1 (en) * 2001-08-24 2004-10-21 Teruo Umemoto Method for preparing polymers containing cyclopentanone structures
JP2018131688A (ja) * 2017-02-16 2018-08-23 Ｊｘｔｇエネルギー株式会社 シス−アルケンの製造装置及び製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120761A (en) * 1977-12-15 1978-10-17 Monsanto Company Electrochemical process for the preparation of acetals of 2-haloaldehydes
US5035777A (en) * 1988-03-07 1991-07-30 Atochem North America, Inc. Preparation of alkanesulfonyl halides and alkanesulfonic acids
US20040206633A1 (en) * 2001-08-24 2004-10-21 Teruo Umemoto Method for preparing polymers containing cyclopentanone structures
JP2018131688A (ja) * 2017-02-16 2018-08-23 Ｊｘｔｇエネルギー株式会社 シス−アルケンの製造装置及び製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BEIJING LI , HAIBO GE: "Highly selective electrochemical hydrogenation of alkynes: Rapid construction of mechanochromic materials", SCIENCE ADVANCES, vol. 5, no. 5, 24 May 2019 (2019-05-24), pages 1 - 7, XP055744341, ISSN: 2375-2548, DOI: 10.1126/sciadv.aaw2774 *
JIN LI, LINGFENG HE, XU LIU, XU CHENG, GUIGEN LI: "Electrochemical Hydrogenation with Gaseous Ammonia", ANGEWANDTE CHEMIE, vol. 131, no. 6, 14 December 2018 (2018-12-14), pages 1773 - 1777, XP055744338, ISSN: 0044-8249, DOI: 10.1002/ange.201813464 *

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