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WO2011026809A1 - Complexes métalliques chiraux et leur utilisation en tant que catalyseurs dans la synthèse de composés organiques - Google Patents

Complexes métalliques chiraux et leur utilisation en tant que catalyseurs dans la synthèse de composés organiques Download PDF

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Publication number
WO2011026809A1
WO2011026809A1 PCT/EP2010/062642 EP2010062642W WO2011026809A1 WO 2011026809 A1 WO2011026809 A1 WO 2011026809A1 EP 2010062642 W EP2010062642 W EP 2010062642W WO 2011026809 A1 WO2011026809 A1 WO 2011026809A1
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radical
group
metal complexes
chiral metal
complexes according
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German (de)
English (en)
Inventor
Olaf Kühl
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Universitaet Greifswald
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Ernst Moritz Arndt Universitaet Greifswald
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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
    • 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
    • C07F15/0046—Ruthenium compounds
    • 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
    • C07F15/04—Nickel compounds
    • 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
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage

Definitions

  • N-heterocyclic carbene ligands Use of monodental non-functionalized N-heterocyclic carbene ligands (NHCs) with chiral centers in the imidazole ring (endocyclic) or in the side chain
  • the NHC have not yet provided the benefits in asymmetric catalysis, which is obtained, for example, when using phosphine ligands.
  • the lagging behind the expectations of the NHC concerns not primarily parameters such as "turnover numbers" or "turnover frequencies". In terms of these parameters, the NHCs are superior to the phosphine ligands.
  • the carbene-based catalysts are usually much more stable and longer active than phosphorus-based catalysts under the drastic reaction conditions of many catalytic reactions.
  • R are the same or different and are open-chain, branched or unbranched or present as part of a ring or ring system and are selected from the group of saturated or unsaturated alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heteroalkyl, heteroalkenyl, heterocycloalkyl, heterocyclo alkylalkyl, cycloalkylheteroalkyl, heterocycloalkyl-heteroalkyl, heteroaryl, heteroaryl arylalkyl, arylheteroalkyl and heteroaryl-heteroalkyl, wherein the heteroatoms from the group of B, Al, Ga, In, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, 0, S, Se and Te are selected and wherein the radicals are unsubstituted or substituted in whole or in part by one or more, identical or different heteroatoms in the form of
  • radicals E are the same or different and wherein R x is the same or
  • R is equal to or different from the radical R and is hydrogen or is selected from the same group as R, or a peptide and / or peptoid chain having 1 to 1000 Amino acids, preferably 1-50 amino acids, wherein a Peptoidech on the nitrogen atom of
  • Peptide bond carries a radical R ';
  • Differentiation means the introduction of asymmetric carbon atoms in the side chain, preferably of the
  • the chiral metal complexes of the formula I according to the invention are preferably characterized in that the radical R has further substituents which are selected from the group of saturated or unsaturated alkyl radical, alkenyl radical, cycloalkyl radical, cycloalkylalkyl radical, aryl radical, arylalkyl radical, heteroalkyl radical, heteroalkenyl radical,
  • Heterocycloalkyl heterocycloalkylalkyl
  • Cycloalkylheteroalkylrest Heterocycloalkylheteroalkylrest, heteroaryl, Heteroarylalkylrest, Arylheteroalkylrest, Heteroarylheteroalkylrest, wherein the heteroatoms from the group of B, Al, Ga, In, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, 0, S, Se and Te are selected, wherein the radicals
  • cyclic and aromatic systems are monovalent rings or multi-membered annelated or isolated rings or form a ring system with the imidazole ring of the structure according to formula I.
  • the radical R is the radical of a naturally occurring or a synthetic amino acid, preferably a naturally occurring amino acid from the ⁇ -carbon atom, which is the D and / or L enantiomers. It is particularly preferred that the radical R is the radical of a proteinogenic amino acid starting from the ⁇ -carbon atom, which is the D and / or L
  • the radical R x is preferably selected from the group of hydrogen, Ci-Ci2-n-alkyl radical, C3-Ci2-branched
  • Ci-Ci2-alkyl radicals which is the same or different substituted by one or more Ci-Ci2-alkyl radicals, Ci-Ci2-heteroalkyl radicals, Ci-Ci2-Heteroalkoxyreste or halogen atoms, wherein the heteroatoms from the group of B, Al, Ga, In, N, P , As, Sb, Bi, Si, Ge, Sn, Pb, O, S, Se and Te are selected and wherein the radicals are unsubstituted or wholly or partially with one or more, identical or different
  • Heteroatoms from the same group in the form of functional group (s) are substituted, wherein the cyclic and aromatic systems are single-membered rings or multi-membered annelated or isolated rings or with the
  • Imidazole ring of the structure according to formula I form a ring system.
  • the radical R " is preferably selected from the group of hydrogen, Ci-Ci2-n-alkyl radical, C3-Ci2-branched
  • Ci-Ci2-alkyl radicals which is unsubstituted or monosubstituted or differently substituted by one or more Ci-Ci2-alkyl radicals, Ci-Ci2-Heteroalkylreste, Ci-Ci2-Alkoxyreste, Ci-Ci2-Hetero alkoxyreste or halogen atoms, whereby the Heteroatome from the group of B, Al, Ga, In, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, O, S, Se and Te are selected and wherein the radicals unsubstituted or wholly or partially with one or multiple, identical or different heteroatoms from the same group in the form of functional group (s)
  • cyclic and aromatic systems are monovalent rings or multi-membered annelated or isolated rings or form a ring system with the imidazole ring of the structure according to formula I.
  • R " is selected from the group of C3-Ci2-cycloalkyl, C 5 - C 4 aryl, C3-Ci2-heterocycloalkyl and C 5 -C aryl group which is unsubstituted or 4 -Hetero- same or is differently substituted by one or more C 1 -C 12 -alkyl radicals, C 1 -C 12 -alkoxy radicals, C 1 -C 12 -heteroalkyl radicals, C 1 -C 12 -heteroalkoxy radicals or halogen atoms, where the heteroatoms from the group of B, Al, Ga, In, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, O, S, Se and Te are selected and wherein the radicals unsubstituted or wholly or partially with one or more, identical or different
  • Heteroatoms from the same group in the form of functional group (s) are substituted, wherein the cyclic and aromatic systems are single-membered rings or multi-membered annelated or isolated rings or with the
  • Imidazole ring of the structure according to formula I form a ring system.
  • the metal M is preferably selected from the group of the metals of the 8th-12th Group of the periodic table selected. Most preferably, the metal M is selected from the group of metals
  • Iron, ruthenium, cobalt, rhodium, iridium, nickel, platinum and palladium Iron, ruthenium, cobalt, rhodium, iridium, nickel, platinum and palladium.
  • the ligand L / ligands L is / are preferably
  • At least one of the ligands L is selected from the group of CO, primary, secondary, tertiary phosphine, primary, secondary, tertiary
  • Phosphite or carbene More preferred is when
  • At least one of the ligands L is selected from the group of primary, secondary, tertiary phosphine, primary, secondary, tertiary phosphite or carbene.
  • at least one of the ligands L is a tricycloalkylphosphane, preferably tricyclohexylphosphane.
  • At least one of the ligands L is a carbene ligand from the group of N-heterocyclic carbene NHC (including CAAC, P- and S-substituted NHC), Fischer carbene or Schrock carbene.
  • N-heterocyclic carbene NHC including CAAC, P- and S-substituted NHC
  • Fischer carbene or Schrock carbene.
  • Ligands L is phenylidene or a substituted phenylidene.
  • the synthesis of the ligands is derived from a
  • Such tuning of the electronic properties of the ligand can be done in several ways.
  • the side chain to the alcohol significantly attenuated the electron-withdrawing effect of the func tional group ⁇ and thus increases the electric ⁇ nenêt corresponding to the metal by reduction of the carboxylic acid. The same takes place in accordance with the reduction of the carboxylic acid amide to the usual amine.
  • Tuning of the steric properties of the ligand can also be done in different ways. For example, by reducing the carbonyl function in the side chain of the NHC not only the elec tronic ⁇ properties, but also the angle at the
  • the position of all substituents of the chelate ring is changed with respect to the metal atom (catalytic center).
  • a modification of the side chain of the amino acid can also be done in different ways.
  • the stereodirecting influence of the chelating ligand is largely determined by the steric demand of the side chain of the original amino acid.
  • the hydrogen atom of glycine for example, has no influence because glycine achiral is.
  • the methyl group and in the phenylalanine a benzyl group (CH 2 C 6 H 5 ).
  • the synthesis of the chiral metal complexes is carried out by reacting the imidazolium compound with a suitable metal complex in the presence of a base, such as
  • Scheme 3 (Preferably having Pincergeometrie) represented by introduction of two functional groups, one in each side chain of the NHC, was in the present invention, a tridentales Chelatcarben that coordinates to ruthenium meridional and so does not substantially alter the structure of the katalyti ⁇ 's center.
  • He ⁇ generation of two chelate the asymmetric centers are fixed sustained in the coordination sphere of the metal catalyst in the side chains of the NHC and thus define the coordination sphere of the catalytic site during catalysis. This is an essential criterion for obtaining an enantiomeric excess.
  • R are the same or different and are open-chain, branched or unbranched or present as part of a ring or ring system and are selected from the group of saturated or unsaturated alkyl radical, Alkenyl radical, cycloalkyl radical, cycloalkylalkyl radical, aryl radical, arylalkyl radical, heteroalkyl radical, heteroalkenyl radical, heterocycloalkyl radical, heterocycloalkylalkyl radical, cycloalkylheteroalkyl radical, heterocycloalkylheteroalkyl radical, heteroaryl radical, heteroarylalkyl radical, arylheteroalkyl radical and heteroaryl-heteroalkyl radical, the heteroatoms being selected from the group of B, Al , Ga, In, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, O, S, Se and Te are selected and wherein the radicals unsubstituted or wholly or partially with one or more,
  • R is equal to or different from the radical R and is hydrogen or is selected from the same group as R, or a peptide and / or peptoid chain having 1 to 1000 Amino acids, preferably 1-50 amino acids, wherein a Peptoidech on the nitrogen atom of Peptide bond carries a radical R ';
  • the chiral metal complexes find as
  • the chiral metal complexes are used as catalyst in the transfer hydrogenation, wherein the use in the asymmetric transfer hydrogenation is preferred.
  • Scheme 4 illustrates the use in cross metathesis (CM) of allylbenzene and 1,4-diacethoxy-2-butene, and in the asymmetric ring-closing metathesis (ARCM) of a prochiral triene:
  • Phe-Im (589 mg, 1.54 mmol) are suspended in 25 ml of THF and treated with nickel (I) acetate (273 mg, 1.54 mmol) and heated to reflux for 12 h. There are 634 mg (84%) of the product as a white powder, which is filtered off, washed and dried.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des complexes métalliques chiraux de la formule générale I et leur utilisation en tant que catalyseur dans la synthèse de composés organiques.
PCT/EP2010/062642 2009-09-07 2010-08-30 Complexes métalliques chiraux et leur utilisation en tant que catalyseurs dans la synthèse de composés organiques Ceased WO2011026809A1 (fr)

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DE102009040234.9 2009-09-07
DE102009040234A DE102009040234A1 (de) 2009-09-07 2009-09-07 Metallkomplexe und deren Verwendung als Katalysator in der Synthese organischer Verbindungen

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN104098607A (zh) * 2014-07-07 2014-10-15 苏州大学 含三环己基膦的单膦单氮杂环卡宾镍(ii)配合物及其应用
CN106966988A (zh) * 2017-04-25 2017-07-21 上海应用技术大学 一种使用微波辐射在水溶液中合成氨基酸咪唑鎓盐的方法
CN115536675A (zh) * 2022-10-10 2022-12-30 郑州大学 一对具有圆偏振发光效应的卡宾保护金纳米团簇及其制备方法和应用

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DE102011054477A1 (de) * 2011-10-13 2013-04-18 Westfälische Wilhelms-Universität Münster Verfahren zur katalytischen Heteroaromatenhydrierung

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US6610626B2 (en) * 2000-09-05 2003-08-26 Cymetech, Llp Highly active metathesis catalysts generated in situ from inexpensive and air stable precursors

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098607A (zh) * 2014-07-07 2014-10-15 苏州大学 含三环己基膦的单膦单氮杂环卡宾镍(ii)配合物及其应用
CN106966988A (zh) * 2017-04-25 2017-07-21 上海应用技术大学 一种使用微波辐射在水溶液中合成氨基酸咪唑鎓盐的方法
CN115536675A (zh) * 2022-10-10 2022-12-30 郑州大学 一对具有圆偏振发光效应的卡宾保护金纳米团簇及其制备方法和应用

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