CN110183498A - A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application - Google Patents

A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application Download PDF

Info

Publication number
CN110183498A
CN110183498A CN201910521749.3A CN201910521749A CN110183498A CN 110183498 A CN110183498 A CN 110183498A CN 201910521749 A CN201910521749 A CN 201910521749A CN 110183498 A CN110183498 A CN 110183498A
Authority
CN
China
Prior art keywords
formula
nitrogen
aryl
chiral
alkyl
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.)
Granted
Application number
CN201910521749.3A
Other languages
Chinese (zh)
Other versions
CN110183498B (en
Inventor
凌飞
侯华萃
陈佳琛
钟为慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201910521749.3A priority Critical patent/CN110183498B/en
Publication of CN110183498A publication Critical patent/CN110183498A/en
Application granted granted Critical
Publication of CN110183498B publication Critical patent/CN110183498B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C07C33/22—Benzylalcohol; phenethyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
    • C07C35/36—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system being a (4.4.0) system, e.g. naphols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
    • C07C35/38—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings derived from the fluorene skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • 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
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • 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
    • 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
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application, shown in the general structure such as formula (I) or formula (II) of the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand:In formula (I) or formula (II): R1、R2It is each independently selected from the alkyl of C1~C6, the naphthenic base of C3~C6, aryl or heterocyclic aryl；R3For the alkyl of aryl, heterocyclic aryl or C1~C6, R4For hydrogen, the alkyl of C1~C6, aryl or heterocyclic aryl；In general structure in formula (I) and formula (II), contain imidazole group or substituted benzimidazole group respectively；Substituent group on the phenyl ring of substituted benzimidazole group is one or more, and each substituent group is each independently selected from the alkyl of H or C1~C4.Chiral ferrocene phosphine nitrogen nitrogen tridentate ligand of the invention have the advantages that it is convieniently synthesized, stable in the air exist, and cheap metal catalyst can be prepared with cheap metal coordination, which has good application in the asymmetric hydrogenation of ketone.

Description

A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application
Technical field
The present invention relates to a kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligands and its preparation method and application.
Background technique
Chiral, secondary alcohols are the important centres such as synthesis of chiral drug, fine chemicals, agricultural chemicals and other special materials Body.Many has gone through clinical listing containing the drug of chiral, secondary alcohols, the first-line treatment drug as patient.Such as: it is used for The treatment gram azoles of ROS1 positive Patients with Non-small-cell Lung replaces Buddhist nun (Crizotinib)；For treating melancholy and anxiety disorder Du Luoxi Spit of fland (Duloxetine)；Etc. (J.Mol.Catal., 2013,27 (2): 99；J.Mol.Catal.,2013,27:507).It is not right Claiming catalytic hydrogenation is to obtain one of chiral alcohol and the most succinct, efficient of other chipal compounds, the method for green.Wherein, chiral The chiral catalyst that ligand and metal complex generate is the core hot spot of asymmetric catalytic hydrogenation research, designs and synthesizes novelty , efficient chiral ligand or chiral catalyst be scientists endeavour research direction (ChemCatChem, 2018,25: 2612；Science,2013,34:1229；Angew.Chem.Int.Ed.,2002,41:1998).However, the height reported at present The metal center of effect chiral catalytic system focuses primarily upon the noble metals such as ruthenium, rhodium, iridium, palladium, and it is expensive, and reserves are rare, and The environmentally friendly cheap metal not as good as preceding transition system, from sustainable development and green chemistry angle, transition before developing It is that cheap metal system has important practical significance.
It is reported that transition metal manganese rich reserves in the earth's crust, be easy to exploit development, it is cheap the advantages that, increasingly by To the attention of scientists.Currently, manganese catalysis asymmetry hydrogenation reaction have been achieved for it is some satisfactory as a result, still phase Compare noble metal catalyst, the disadvantages of it is low that there are still catalytic activity, and stereoselectivity is not high, and the substrate scope of application is limited (Acc.Chem.Res.,2015,48:1979；Acc.Chem.Res.,2018,51:1558；Synthesis,2017,49: 3377).Therefore, novel chiral ligand is designed and synthesized, the change of the latent chipal compounds of high efficiency regulatory is carried out with cheap metal complexing , region, stereoselectivity have important practical significance.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of chiral ferrocene phosphine nitrogen nitrogen Tridentate ligand and its preparation method and application, which has simple synthetic method, in air In be stabilized, be easy to large scale preparation, and cheap metal catalyst can be prepared with cheap metal coordination, be applied to asymmetric anti- The advantages that answering.
The chiral ferrocene phosphine nitrogen nitrogen tridentate ligand, it is characterised in that its general structure such as formula (I) or formula (II) institute Show:
In formula (I) or formula (II): R1、R2Be each independently selected from the alkyl of C1~C6, the naphthenic base of C3~C6, aryl or Heterocyclic aryl；R3For the alkyl of aryl, heterocyclic aryl or C1~C6, R4For hydrogen, the alkyl of C1~C6, aryl or heterocyclic aryl；
In general structure in the formula (I) and formula (II), contain imidazole group or substituted benzimidazole group respectively；Institute The substituent group on the phenyl ring of substituted benzimidazole group is stated as one or more, each substituent group is each independently selected from H or C1 The alkyl of~C4.
The compound of formula (I) general structure, specific molecular structural formula are any one in formula (I-1)~formula (I-7) It is shown:
The compound of formula (II) general structure, specific molecular structural formula are shown in formula (II-1):
The preparation method of the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand, it is characterised in that include the following steps: nitrogen It, will chiral phosphine ferrocene-α-ethamine as shown in formula (III) or formula (IV) and the carbonylation of the imidazoles as shown in formula (V) under protection It closes object to be dissolved in alcohols solvent, be reacted 1-24 hours at 20-80 DEG C, after TLC tracks to fully reacting, at -20-60 DEG C Sodium borohydride is added, and the reaction was continued 1-12 hours；After reaction, recycling design, concentrated residues object warp is concentrated under reduced pressure in reaction solution Column chromatography for separation obtains the chiral ferrocene nitrogen nitrogen phosphine tridentate ligand as shown in formula (I) or formula (II)；
In formula (III) or formula (IV), R1、R2It is each independently selected from the alkyl of C1~C6, the naphthenic base of C3~C6, aryl Or heterocyclic aryl；
In formula (V), R3For the alkyl of aryl, heterocyclic aryl or C1~C6, R4For hydrogen, the alkyl of C1~C6, aryl or heterocycle Aryl；
In the general structure of the formula (V), contain imidazole group or substituted benzimidazole group；The substituted benzimidazole Substituent group on the phenyl ring of group is one or more, and each substituent group is each independently selected from the alkyl of H or C1~C4.
Further, the chiral phosphine ferrocene-α-ethamine as shown in formula (III) or formula (IV), miaow shown in formula (V) The ratio between amount of substance of azoles carbonyls, sodium borohydride is 1:1.0~1.5:2.0~5.0；The alcohols solvent is first Alcohol, ethyl alcohol or isopropanol.
The preparation method of the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand, reaction formula are as follows:
The chiral ferrocene phosphine nitrogen nitrogen tridentate ligand is preparing the application in cheap metal catalyst, it is characterised in that By the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and cheap metal complex compound hybrid reaction, the cheap metal catalysis is made Agent.
Further, the cheap metal complex compound is Mn (CO)5Br。
Further, the ratio between amount of substance of the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and cheap metal complex compound is 1: 1.0~2.0, preferably 1:1.1.
Application of the cheap metal catalyst in the asymmetric hydrogenation of ketone, reaction formula are as follows:
Compared with the existing technology, the beneficial effect that the present invention obtains is:
1) chiral ferrocene phosphine nitrogen nitrogen tridentate ligand provided by the invention is convieniently synthesized, stable in the air, is suitble to big rule Mould preparation.Preferable activity and enantioselectivity are shown to C=O bond, there is important researching value and application prospect.
2) chiral ferrocene phosphine nitrogen nitrogen tridentate ligand provided by the invention can be made with cheap metal complex compound hybrid reaction Obtain cheap metal catalyst.The cheap metal catalyst has good application in the asymmetric hydrogenation of ketone, including not right Claim hydrogenation, Asymmetric hydrogen transfer reaction, Asymmetric hydrosilylation, asymmetric hydroboration.
3) under the cheap metal catalyst, aralkyl ketone can be added under alkaline condition with hydrogen donor Hydrogen reduction.Ligand and metal are the cores of catalysis reaction, can generate significant impact to reaction by the fine tuning to ligand environment, Therefore the adjustability of ligand largely determines the substrate scope of application of catalyst, and different substrates may need difference Steric hindrance and electrical ligand realize high response and highly selective to be catalyzed.Ligand of the invention in steric hindrance and electrical property all It is highly susceptible to regulating and controlling, therefore there is the extensive substrate scope of application.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1: the preparation of chiral ligand I-1
It is added shown in compound (4.13g, 10.0mmol) shown in formula (III-1) and formula (V-1) into 100mL three-necked flask Under nitrogen protection, 50mL methanol is added in compound (2.05g, 11.0mmol), after react 5 hours at 80 DEG C, is cooled to 60 DEG C directly It connects and sodium borohydride (1.5g, 40mmol) reaction 4h is added.Recycling methanol, concentrated residues are concentrated under reduced pressure in reaction solution by end of reaction Object obtains orange/yellow solid chiral ligand I-1 (4.1g, yield 71%), mp 82-83 DEG C, [α] through column chromatography for separationD 20=125.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-1:1H NMR(600MHz,CDCl3)δ7.57-7.55(m,2H),7.41-7.37 (m,3H),7.25-7.23(m,2H),7.19-7.17(m,2H),7.16-7.15(m,2H),6.88-6.86(m,3H),6.66 (s, 1H), 5.29 (s, 1H), 4.77 (d, J=16.2Hz, 1H), 4.58 (d, J=16.2Hz, 1H), 4.48 (s, 1H), 4.31 (s,1H),4.09-4.08(m,1H),3.94(s,5H),3.86(s,1H),3.67-3.66(m,1H),3.58-3.56(m,1H), 3.49-3.47(m,1H),3.11-3.09(m,1H),1.50-1.49(m,3H).13C NMR(150MHz,CDCl3)δ146.4, 136.8,135.2 (d, J=21.3Hz), 135.1 (d, J=17.7Hz), 132.4,132.3,129.1,128.6,128.1, 128.0,127.9,127.7,127.5,126.8,125.2,124.9,120.3,117.4,112.3,71.1,69.5,69.2, 68.9,53.3,52.1,48.8,43.1,29.6,28.4,19.9.31P NMR(162MHz,CDCl3)δ-23.25.HRMS(ESI) calcd for C35H34FeN3P[M+H]+:584.1913,found:584.1821。
Embodiment 2: the preparation of chiral ligand I-2
Toward chemical combination shown in compound (4.13g, 10.0mmol) shown in 100mL three-necked flask Chinese style (III-1) and formula (V-2) Object (2.36g, 10.0mmol) under nitrogen protection, is added 50mL ethyl alcohol and boron is added after being cooled to 0 DEG C after reacting 12h at 50 DEG C Sodium hydride (1.1g, 30mmol) reacts 8h.Recycling ethyl alcohol is concentrated under reduced pressure in reaction solution by end of reaction, and concentrated residues object is through column layer Analysis separates to obtain orange/yellow solid chiral ligand I-2 (4.7g, yield 75%).mp 84-85℃,[α]D 20=120.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-2:1H NMR(600MHz,CDCl3) δ 7.71 (d, J=7.8Hz, 1H), 7.55- 7.53(m,2H),7.21-7.36(m,3H),7.21-7.14(m,8H),7.09-7.07(m,3H),7.02-6.99(m,1H), 6.85-6.83 (m, 2H), 5.03 (d, J=16.8Hz, 1H), 4.87 (d, J=16.8Hz, 1H), 4.48 (s, 1H), 4.31 (s, 1H), 4.17-4.15 (m, 1H), 3.95 (s, 5H), 3.86 (s, 1H), 3.74 (d, J=13.8Hz, 1H), 3.65 (d, J= 13.8Hz, 1H), 1.52 (d, J=6.6Hz, 3H)13C NMR(150MHz,CDCl3) δ 153.1,142.4,140.5 (d, J= 10.5Hz), 137.6 (d, J=9.0Hz), 136.6,135.7,135.3,135.1,132.5,132.4,129.2,128.7, 128.2,128.12,128.07,127.8,127.5,126.3,122.4,121.8,119.5 109.6,97.8 (d, J= 25.5Hz), 75.0 (d, J=9.0Hz), 71.3 (d, J=4.5Hz), 69.7,69.3,69.0 (d, J=4.5Hz), 51.4 (d, J =9.0Hz), 46.4,44.0,20.0.31PNMR(162MHz,CDCl3)δ-24.25.HRMS(ESI)calcd for C39H36FeN3P[M+H]+:634.2069,found:634.1996。
Embodiment 3: the preparation of chiral ligand I-4
Toward chemical combination shown in compound (4.13g, 10.0mmol) shown in 100mL three-necked flask Chinese style (III-1) and formula (V-3) Under nitrogen protection, 50mL isopropanol is added, after reacting 24 hours at 80 DEG C, after being cooled to -20 DEG C in object (4.59g, 15.0mmol) Sodium borohydride (1.9g, 50mmol) is added and reacts 10h.Recycling isopropanol, concentrated residues are concentrated under reduced pressure in reaction solution by end of reaction Object obtains orange/yellow solid chiral ligand I-4 (4.4g, yield 57%) through column chromatography for separation.mp 83–84℃,[α]D 20=125.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-4:1H NMR(400MHz,CDCl3) δ 7.76 (d, J=8.0Hz, 1H), 7.57- 7.53 (m, 3H), 7.41-7.37 (m, 3H), 7.35 (d, J=7.6Hz, 2H), 7.28 (d, J=7.6Hz, 1H), 7.24-7.20 (m, 2H), 7.18-7.09 (m, 4H), 6.87 (d, J=8.0Hz, 1H), 4.46 (s, 1H), 4.28 (s, 1H), 4.21 (s, 1H), 4.04(s,5H),3.80(s,1H),3.43-3.34(m,2H),1.94-1.89(m,1H),1.79-1.77(m,1H),1.49(d, J=6.4Hz, 3H), 1.10 (d, J=6.8Hz, 6H), 0.95 (d, J=6.8Hz, 6H)13C NMR(100MHz,CDCl3)δ 153.7,147.5,147.4,142.4,137.5,137.1,135.1,134.9,132.4,132.2,130.1,129.0, 128.2,128.2,128.1,128.0,124.3,122.4,121.8,119.5,110.1,75.0,74.9,71.0,70.2, 69.6,68.8,68.5,60.4,51.5,51.5,43.5,28.1,28.1,25.1,23.6,23.5,21.2,21.0,14.2.31P NMR(162MHz,CDCl3)δ-24.92.HRMS(ESI)calcd forC44H46FeN3P[M+H]+:704.2852,found: 704.2851。
Embodiment 4: the preparation of chiral ligand I-5
Toward chemical combination shown in compound (4.13g, 10.0mmol) shown in 100mL three-necked flask Chinese style (III-1) and formula (V-4) Object (2.75g, 11.0mmol) under nitrogen protection, is added 50mL methanol and is directly added into hydroboration after reacting 24 hours at 20 DEG C Sodium (0.76g, 20mmol) reacts 8h.Recycling methanol is concentrated under reduced pressure in reaction solution by end of reaction, and concentrated residues object is through column chromatography point From orange/yellow solid chiral ligand I-5 (4.2g, yield 72%).mp 88-89℃,[α]D 20=120.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-5:1H NMR(400MHz,CDCl3)δ7.62-7.57(m,2H),7.47(s,1H), 7.42-7.41 (s, 3H), 7.28-7.24 (t, J=7.2Hz, 2H), 7.19-7.16 (m, 2H), 7.12-7.11 (m, 1H), 6.97 (s,1H),4.56(s,1H),4.37-4.36(m,1H),4.23-4.16(m,1H),4.01(s,5H),3.92(s,1H),3.80- 3.68 (m, 2H), 3.29 (s, 3H), 2.41-2.39 (d, J=4.8Hz, 6H), 1.60-1.58 (d, J=6.4Hz, 3H)13C NMR(100MHz,CDCl3)δ151.9,140.6,140.16,140.1,137.4,137.3,134.9,134.8,134.4, 132.3,132.1,130.8,130.0,128.9,128.0,127.9,127.8,127.7,119.2,109.0,97.8,97.6, 77.2,76.8,76.5,71.0,69.4,69.1,68.9,60.2,51.2,43.6,29.1,20.3,20.0,19.9.31P NMR (162MHz,CDCl3)δ-24.75.HRMS(ESI)calcd for C35H36FeN3P[M+H]+:586.2069；Found: 586.1976.
Embodiment 5: the preparation of chiral ligand I-6
Toward compound shown in compound (4.67g, 10mmol) shown in 100mL three-necked flask Chinese style (III-2) and formula (V-2) (2.59g, 11.0mmol) under nitrogen protection, is added 50mL methanol and is directly added into sodium borohydride after reacting 12h at 50 DEG C (1.1g, 30mmol) reacts 6h.Recycling methanol is concentrated under reduced pressure in reaction solution by end of reaction, and concentrated residues object is through column chromatography for separation It obtains orange/yellow solid chiral ligand I-6 (4.1g, yield 57%).mp 79-80℃,[α]D 20=125.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-6:1H NMR(400MHz,CDCl3) 7.71-7.69 (d, J=7.6Hz, 1H), (7.24-7.23 m, 7H), 7.09-7.07 (m, 1H), 6.99 (s, 1H), 6.87-6.85 (m, 2H), 6.80-6.78 (d, J= 7.2Hz,2H),6.59(s,1H),5.05-4.90(m,2H),4.46(s,1H),4.28(s,1H),4.20-4.11(m,1H), 3.97(s,5H),3.84(s,1H),3.72-3.61(m,2H),2.60-2.54(m,1H),2.31(s,6H),2.02(s,6H), 1.50-1.48 (d, J=6.4Hz, 3H)13CNMR(100MHz,CDCl3)δ153.0,142.3,139.7,139.6,137.3, 137.2,137.1,137.1,137.0,136.9,136.4,135.5,132.7,132.5,130.5,130.0,129.9, 129.6,128.5,127.2,126.1,122.0,121.4,119.3,109.3,97.5,97.3,75.3,71.2,69.4, 68.7,51.4,51.3,46.2,46.0,43.8,29.5,21.1,20.9,19.7,11.1.31P NMR(162MHz,CDCl3)δ- 24.11.HRMS(ESI)calcd for C43H44FeN3P[M+H]+:690.2695,found:690.2213。
Embodiment 6: the preparation of chiral ligand I-7
Toward compound shown in compound (3.45g, 10mmol) shown in 100mL three-necked flask Chinese style (III-3) and formula (V-2) (2.59g, 11.0mmol) under nitrogen protection, is added 50mL methanol and is directly added into sodium borohydride after reacting 12h at 50 DEG C 4h is reacted under (1.1g, 30mmol).Recycling methanol is concentrated under reduced pressure in reaction solution by end of reaction, and concentrated residues object is through column chromatography point From orange/yellow solid chiral ligand I-7 (3.5g, yield 62%).mp 84-85℃,[α]D 20=121.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand I-7:1H NMR(400MHz,CDCl3):δ7.74-7.72(m,1H),7.22-7.20 (m, 2H), 7.05-7.04 (m, 2H), 5.48 (d, J=8.0Hz, 2H), 4.39 (s, 1H), 4.28 (s, 1H), 4.23 (s, 1H), 4.14-4.13 (m, 7H), 4.01-3.99 (m, 1H), 3.91 (s, 2H), 1.54 (d, J=6.4Hz, 3H), 1.41-1.30 (m, 9H), 1.25 (s, 2H), 1.03-0.98 (dd, J=13.2,6.8Hz, 3H), 0.77-0.72 (dd, J=14.0,6.8Hz, 3H) .13C NMR(100MHz,CDCl3)δ153.2,142.3,136.2,135.6,128.6,127.4,126.2,122.3,121.6, 119.4,109.4,97.4,70.6,69.9,69.3,68.3,67.3,50.9 (d, J=9.0Hz), 46.8,43.6,29.5, 25.9 (d, J=13.0Hz), 24.9 (d, J=10.0Hz), 24.8,22.7,22.5,21.0,20.8,20.1,19.9, 19.2.31PNMR(162MHz,CDCl3)δ-9.15.HRMS(ESI)calcd for C33H40FeN3P[M+H]+:566.2382, found:566.2388。
Embodiment 7: the preparation of chiral ligand II-1
Toward chemical combination shown in compound (4.13g, 10.0mmol) shown in 100mL three-necked flask Chinese style (IV-1) and formula (V-5) Object (1.76g, 11.0mmol) under nitrogen protection, is added 50mL methanol and is directly added into hydroboration after reacting 24 hours at 50 DEG C 4h is reacted under sodium (1.1g, 30mmol).Recycling methanol is concentrated under reduced pressure in reaction solution by end of reaction, and concentrated residues object is chromatographed through column Separate to obtain orange/yellow solid chiral ligand II-1 (4.17g, yield 75%).mp 90-92℃,[α]D 20=125.0 (c=0.5, CHCl3)。
The characterize data of chiral ligand II-1:1H NMR(400MHz,Chloroform-d):δ7.76(s,1H),7.64 (s, 2H), 7.46 (s, 3H), 7.28 (m, 5H), 7.19 (t, J=6.8Hz, 2H), 7.11 (m, 1H), 4.61 (s, 1H), 4.42 (s, 1H), 4.31-4.28 (m, 1H), 4.07 (s, 5H), 3.97 (s, 1H), 3.86 (d, J=14.0Hz, 1H), 3.78 (d, J= 14.0Hz, 1H) 3.38 (s, 3H), 1.66 (d, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ152.6,141.9, 139.9,139.8,137.2,137.1,135.7,134.9,134.7,132.2,132.0,128.8,127.8,127.5, 121.8,121.3,119.0,108.6,97.5,97.3,74.6,74.6,71.0,69.9,69.3,69.0,68.8,51.0, 43.4,29.0,19.8.31P NMR(162MHz,CDCl3)δ-24.91.HRMS(ESI)calcd for C33H32FeN3P[M+H]+: 558.1756,found:558.1668。
Embodiment 8:(R)-benzyl carbinol 2A preparation
(1) by chiral ligand I-1 (5.8mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) by compound (240mg, 2mmol) shown in formula (1A), lithium hydroxide (1.0mg, 0.04mmol), isopropanol The cheap metal catalyst of (2mL), step (1) preparation sequentially add in the hydrogenation bottle of 5mL, and hydrogenation bottle is put into hydrogenation reaction cauldron In, hydrogen replaces the H for being filled with 3Mpa pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution is through silicon Diatomaceous earth filtering, detects filtrate: the conversion ratio that GC measures compound shown in formula (1A) is that 99%, HPLC measures reaction product The enantioselectivity ee value of compound shown in formula (2A) is 54.5%.It is surveyed using HPLC Chiralpak OJ-H chiral chromatographic column Determine enantiomeric excess, n-hexane: isopropanol=90:10 (v/v)；Flow velocity=0.8mL/min；UV is detected in 220nm；tR(S)= 10.45min(minor),tR(R)=11.77min (major).
Embodiment 9:(R)-benzyl carbinol 2A preparation
(1) by chiral ligand I-2 (6.3mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) by compound (1.2g, 10mmol) shown in formula (1A), lithium hydroxide (5mg, 0.2mmol), isopropanol The cheap metal catalyst of (10mL), step (1) preparation sequentially add in the hydrogenation bottle of 25mL, and hydrogenation bottle is put into hydrogenation In kettle, hydrogen replaces the H for being filled with 3Mpa pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution warp Diatomite filtering, detects filtrate: the conversion ratio that GC measures compound shown in formula (1A) is that 99%, HPLC measurement reaction produces The enantioselectivity ee value of compound shown in object formula (2A) is 73.3%.
Embodiment 10:(R)-benzyl carbinol 2A preparation
(1) by chiral ligand I-5 (5.8mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) compound (1.20g, 10mmol) shown in modus ponens (1A), lithium hydroxide (5mg, 0.2mmol), isopropanol The cheap metal catalyst of (10mL), step (1) preparation sequentially add in the hydrogenation bottle of 25mL, and hydrogenation bottle is put into hydrogenation In kettle, hydrogen replaces the H for being filled with 3Mpa pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution warp Diatomite filtering, detects filtrate: the conversion ratio that GC measures compound shown in formula (1A) is that 99%, HPLC measurement reaction produces The enantioselectivity ee value of compound shown in object formula (2A) is 65.2%.
Embodiment 11:(R)-benzyl carbinol 2A preparation
(1) by chiral ligand I-6 (6.9mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) compound (1.20g, 10mmol) shown in modus ponens (1A), lithium hydroxide (5mg, 0.2mmol), isopropanol The cheap metal catalyst of (10mL), step (1) preparation are added in the hydrogenation bottle of 25mL, and hydrogenation bottle is put into hydrogenation reaction cauldron In, hydrogen replaces the H for being filled with 3Mpa pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution is through silicon Diatomaceous earth filtering, detects filtrate: the conversion ratio that GC measures compound shown in formula (1A) is that 99%, HPLC measures reaction product The enantioselectivity ee value of compound shown in formula (2A) is 58.2%.
Embodiment 12:(S)-benzyl carbinol 2A ' preparation
(1) by chiral ligand II-1 (5.7mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) compound (1.20g, 10mmol) shown in modus ponens (1A), lithium hydroxide (0.5mg, 0.02mmol), ethyl alcohol The cheap metal catalyst of (2mL), step (1) preparation sequentially add in the hydrogenation bottle of 5mL, and hydrogenation bottle is put into hydrogenation reaction cauldron In, hydrogen replaces the H for being filled with 30atm pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution warp Diatomite filtering, detects filtrate: GC measures the conversion ratio 99% of compound shown in formula (1A), and HPLC measures reaction product The enantioselectivity ee value (- 71.2%) of compound shown in formula (2A ').
Embodiment 13-23: the preparation of chiral, secondary alcohols (R) -2B~2L
(1) by chiral ligand I-2 (6.3mg, 0.011mmol), Mn (CO)5Reaction is added in Br (3.0mg, 0.01mmol) In bottle, DMF (2mL) is added under argon atmosphere, after return stirring is stayed overnight, it is extra that reaction solution is concentrated to removing in high vacuum conditions It is spare that cheap metal catalyst is made in solvent.
(2) aryl methyl ketone compound 1B-1L (10mmol) is taken, lithium hydroxide (5mg, 0.2mmol), isopropanol (10mL), The cheap metal catalyst of step (1) preparation sequentially adds in the hydrogenation bottle of 25mL, hydrogenation bottle is put into hydrogenation reaction cauldron, hydrogen Gas replaces the H for being filled with 3Mpa pressure afterwards three times2, 10h is reacted at room temperature.After end of reaction discharges hydrogen, reaction solution is through diatomite Filtering, detects filtrate: GC measures the conversion ratio of 1B-1L, and HPLC measures the enantioselectivity ee of reaction product 2B-2L Value.Concrete outcome is as follows:
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered When the concrete form for being seen as limited by embodiment and being stated.

Claims (8)

1. a kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand, it is characterised in that shown in its general structure such as formula (I) or formula (II):
In formula (I) or formula (II): R1、R2It is each independently selected from the alkyl of C1~C6, the naphthenic base of C3~C6, aryl or heterocycle Aryl；R3For the alkyl of aryl, heterocyclic aryl or C1~C6, R4For hydrogen, the alkyl of C1~C6, aryl or heterocyclic aryl；
In general structure in the formula (I) and formula (II), contain imidazole group or substituted benzimidazole group respectively；It is described to take It is one or more for the substituent group on the phenyl ring of benzimidazole group, each substituent group is each independently selected from H or C1~C4 Alkyl.
2. a kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand as described in claim 1, it is characterised in that formula (I) general structure Compound, specific molecular structural formula is shown in any one in formula (I-1)~formula (I-7):
3. a kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand as described in claim 1, it is characterised in that formula (II) general structure Compound, specific molecular structural formula be formula (II-1) shown in:
4. a kind of preparation method of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand as described in claim 1, it is characterised in that including Following steps:, will chiral phosphine ferrocene-α-ethamine as shown in formula (III) or formula (IV) and as shown in formula (V) under nitrogen protection Imidazole carbonyl compound be dissolved in alcohols solvent, reacted 1-24 hours at 20-80 DEG C, after TLC tracks to fully reacting, Sodium borohydride is added at -20-60 DEG C, and the reaction was continued 1-12 hours；After reaction, recycling design is concentrated under reduced pressure in reaction solution, Concentrated residues object obtains the chiral ferrocene nitrogen nitrogen phosphine tridentate ligand as shown in formula (I) or formula (II) through column chromatography for separation；
In formula (III) or formula (IV), R1、R2It is each independently selected from the alkyl of C1~C6, the naphthenic base of C3~C6, aryl or miscellaneous Cyclophane base；
In formula (V), R3For the alkyl of aryl, heterocyclic aryl or C1~C6, R4For hydrogen, the alkyl of C1~C6, aryl or heterocycle virtue Base；
In the general structure of the formula (V), contain imidazole group or substituted benzimidazole group；The substituted benzimidazole group Phenyl ring on substituent group be one or more, each substituent group is each independently selected from the alkyl of H or C1~C4.
5. the preparation method of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand as claimed in claim 4, it is characterised in that it is described as Chiral phosphine ferrocene-α-ethamine shown in formula (III) or formula (IV), imidazole carbonyl compound, sodium borohydride shown in formula (V) The ratio between amount of substance is 1:1.0~1.5:2.0~5.0；The alcohols solvent is methanol, ethyl alcohol or isopropanol.
6. the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand as described in claims 1 to 3 any one is preparing cheap metal catalysis Application in agent, it is characterised in that by the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and cheap metal complex compound hybrid reaction, The cheap metal catalyst is made.
7. application as claimed in claim 6, it is characterised in that the cheap metal complex compound is Mn (CO)5Br。
8. application as claimed in claim 6, it is characterised in that the chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and cheap metal The ratio between amount of substance of complex compound is 1:1.0~2.0, preferably 1:1.1.
CN201910521749.3A 2019-06-17 2019-06-17 Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof Active CN110183498B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910521749.3A CN110183498B (en) 2019-06-17 2019-06-17 Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910521749.3A CN110183498B (en) 2019-06-17 2019-06-17 Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110183498A true CN110183498A (en) 2019-08-30
CN110183498B CN110183498B (en) 2022-04-29

Family

ID=67722041

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910521749.3A Active CN110183498B (en) 2019-06-17 2019-06-17 Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110183498B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875474A (en) * 2020-07-30 2020-11-03 浙江工业大学 Preparation method of (R, E) -4-phenylbutyl-3-ene-2-alcohol derivative

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103012498A (en) * 2012-01-10 2013-04-03 中国人民解放军第四军医大学 Chiral ferrocene tridentate ligand and preparation method thereof as well as application in asymmetric hydrogenation reaction catalysis
CN107522751A (en) * 2016-06-21 2017-12-29 中国科学院大连化学物理研究所 A kind of high steric-hindrance amino chiral ferrocene P, N, N part and preparation method and application
CN108774271A (en) * 2018-02-08 2018-11-09 浙江工业大学 A kind of chiral nitrogen nitrogen phosphine tridentate ligand and its application based on ferrocene frame having ferrocene frame

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103012498A (en) * 2012-01-10 2013-04-03 中国人民解放军第四军医大学 Chiral ferrocene tridentate ligand and preparation method thereof as well as application in asymmetric hydrogenation reaction catalysis
CN107522751A (en) * 2016-06-21 2017-12-29 中国科学院大连化学物理研究所 A kind of high steric-hindrance amino chiral ferrocene P, N, N part and preparation method and application
CN108774271A (en) * 2018-02-08 2018-11-09 浙江工业大学 A kind of chiral nitrogen nitrogen phosphine tridentate ligand and its application based on ferrocene frame having ferrocene frame

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FEI LING ET AL.: "Highly Enantioselective Synthesis of Chiral Benzhydrols via Manganese Catalyzed Asymmetric Hydrogenation of Unsymmetrical Benzophenones Using an Imidazole-Based Chiral PNN Tridentate Ligand", 《ORGANIC LETTERS》 *
JOSE R. CABRERO-ANTONINO ET AL.: "Efficient Base-Free Hydrogenation of Amides to Alcohols and Amines Catalyzed by Well-Defined Pincer Imidazolyl-Ruthenium Complexes", 《ACS CATALYSIS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875474A (en) * 2020-07-30 2020-11-03 浙江工业大学 Preparation method of (R, E) -4-phenylbutyl-3-ene-2-alcohol derivative
CN111875474B (en) * 2020-07-30 2022-10-04 浙江工业大学 Preparation method of (R, E) -4-phenylbutyl-3-ene-2-alcohol derivative

Also Published As

Publication number Publication date
CN110183498B (en) 2022-04-29

Similar Documents

Publication Publication Date Title
Bette et al. New developments in zinc-catalyzed asymmetric hydrosilylation of ketones with PMHS
Focken et al. Synthesis of iridium complexes with new planar chiral chelating phosphinyl-imidazolylidene ligands and their application in asymmetric hydrogenation
Chelucci et al. Ruthenium and osmium complexes containing 2-(aminomethyl) pyridine (Ampy)-based ligands in catalysis
CN108774271B (en) Chiral nitrogen phosphine tridentate ligand based on ferrocene skeleton and application thereof
Bolm et al. Synthesis of iridium complexes with novel planar chiral chelating imidazolylidene ligands
Liu et al. Highly efficient and convenient asymmetric hydrosilylation of ketones catalyzed with zinc Schiff base complexes
WO2011135753A1 (en) Ruthenium complex and method for preparing optically active alcohol compound
Hong et al. Synthesis of planar chiral imidazo [1, 5-a] pyridinium salts based on [2.2] paracyclophane for asymmetric β-borylation of enones
Royo Recent advances in catalytic hydrosilylation of carbonyl groups mediated by well-defined first-row late transition metals
Naziruddin et al. Ruthenium (II) carbonyl complexes bearing CCC-pincer bis-(carbene) ligands: synthesis, structures and activities toward recycle transfer hydrogenation reactions
Leñero et al. Heterolytic activation of dihydrogen by platinum and palladium complexes
Haberberger et al. Synthesis, Characterization and Catalytic Application of Iron Complexes Modified by Monodentate Phosphane Ligands
Abubakar et al. Transfer hydrogenation of ketones catalyzed by a trinuclear Ni (II) complex of a Schiff base functionalized N-heterocyclic carbene ligand
Giboulot et al. Cyclometalated dicarbonyl ruthenium catalysts for transfer hydrogenation and hydrogenation of carbonyl compounds
US20140243543A1 (en) Iron(ii) catalysts containing diimino-diphosphine tetradentate ligands and their synthesis
Lu et al. Highly enantioselective catalytic alkynylation of ketones–A convenient approach to optically active propargylic alcohols
CN114080379B (en) Hydrogenation of esters to alcohols in the presence of Ru-PNN complexes
Song et al. Synthesis, structure, and catalytic activity of rhodium complexes with new chiral binaphthyl-based NHC-ligands
US9556211B2 (en) Metal complex compound, hydrogen production catalyst and hydrogenation reaction catalyst each comprising the metal complex compound, and hydrogen production method and hydrogenation method each using the catalyst
Monguchi et al. Catalytic asymmetric conjugate reduction with ethanol: A more reactive system Pd (II)–iPr-DUPHOS complex with molecular sieves 4A
CN112851479B (en) Method for preparing chiral alkyl compound by catalyzing asymmetric hydrogenation reaction of olefin with iron complex catalyst
CN110183498A (en) A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application
Gadenne et al. Easily recoverable BINOL ligand with ionic tag for asymmetric catalysis
Kuil et al. Rigid bis-zinc (II) salphen building blocks for the formation of template-assisted bidentate ligands and their application in catalysis
Schmid et al. Mechanistic and stereochemical aspects of the asymmetric cyclocarbonylation of 1, 6-enynes with rhodium catalysts

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