CN111320646B - 1, 4-eneyne compound and preparation method and application thereof - Google Patents

1, 4-eneyne compound and preparation method and application thereof Download PDF

Info

Publication number
CN111320646B
CN111320646B CN201910829333.8A CN201910829333A CN111320646B CN 111320646 B CN111320646 B CN 111320646B CN 201910829333 A CN201910829333 A CN 201910829333A CN 111320646 B CN111320646 B CN 111320646B
Authority
CN
China
Prior art keywords
compound
formula
reaction
eneyne
nmr
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
Application number
CN201910829333.8A
Other languages
Chinese (zh)
Other versions
CN111320646A (en
Inventor
李先纬
饶建行
欧阳文森
钟伟键
廖桂兰
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201910829333.8A priority Critical patent/CN111320646B/en
Publication of CN111320646A publication Critical patent/CN111320646A/en
Application granted granted Critical
Publication of CN111320646B publication Critical patent/CN111320646B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Landscapes

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

Abstract

The invention relates to the technical field of organic synthesis, in particular to a 1, 4-eneyne compound and a preparation method and application thereof. The invention discloses a 1, 4-eneyne compound which has a structure shown in a formula (I), wherein R 1 、R 2 And R 3 Each independently selected from hydrogen, alkyl, benzene ring, naphthalene or heteroaromatic ring, R 4 Is hydrogen or silicon based. The 1, 4-eneyne compound provided by the invention widens the variety of the 1, 4-eneyne compound. The 1, 4-eneyne compounds are molecules containing unsaturated carbon-carbon double bonds and carbon-carbon triple bonds, contain a plurality of functional groups which can be conveniently transformed, such as silicon bases which are directly connected with carbon-carbon triple bonds of alkyne and can be conveniently removed, so that terminal alkyne can be obtained, and the compounds have the potential of being efficiently transformed into complex molecules containing heterocycles and a plurality of unsaturated bonds through C-H transformation of the terminal alkyne, nucleophilic metallization reaction of the alkyne, cycloisomerization of the eneyne and other reactions, and can be widely applied to organic synthesis and materialsIn the preparation of materials and medicaments.

Description

1, 4-eneyne compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a 1, 4-eneyne compound and a preparation method and application thereof.
Background
The carbon-carbon unsaturated bond compound comprises common alkene and alkyne, and is necessary for production and life of people due to pi bonds which are easy to chemically convert. Petroleum refining and restructuring are currently important sources for the widespread production of olefins, and the development of highly efficient multi-functionalized olefins and the introduction of olefins into molecules has been one of the core research topics in organic chemistry and related material chemistry, pharmaceutical chemistry.
Just because of the inexorable position of olefins in modern people's production, the Nobel prize of the scientific community has been issued to many fields of olefin-based synthesis and conversion, such as 1950, and the Diels-Alder reaction can be used as a powerful means for constructing a continuous chiral center with high efficiency and high selectivity by the D-A reaction of dienophile and diene to obtain the Nobel chemical prize; ziegler and natta olefin polymerization catalyst studies achieved the nobel prize in 1963; in addition, the nobel chemical prize in 1979 awards the hydroboration reaction of olefins developed by Brown and the build-up of olefins by carbonyl via ylide reaction with phosphines discovered by Wititg. In 2001, the prize of chemical nobel was awarded to hopplece and feiyeliang based on the catalytic asymmetric synthesis reaction of unsaturated bonds; the 2005 prize of nobel's chemistry awarded the field of olefin metathesis, rewarding it to provide more opportunities for the chemical synthesis of complex molecules; in 2010, nobel's chemistry awarded a palladium-catalyzed coupling reaction, where an important one of the conversions was palladium-catalyzed conversion of a terminal olefin to a multi-substituted olefin compound by coupling with a halogenated hydrocarbon. Therefore, the method has important significance for the chemical and chemical fields by selectively converting the olefin and further realizing the high-efficiency high-added-value conversion of the simple olefin.
In addition, alkynes are widely used in the field of organic functional materials due to their unique physical properties such as rigidity and optical properties of carbon-carbon triple bonds. In addition, alkynes, which are important synthons in organic synthesis, can rapidly construct synthetic intermediates through nucleophilic addition and electrophilic addition reactions.
Considering the carbon-carbon triple bond and the important role of olefin in organic chemistry, the selective introduction of multifunctional alkynyl fragments into olefin molecules broadens the variety of 1, 4-eneyne compounds and has important synthetic significance.
Disclosure of Invention
In view of this, the invention provides a 1, 4-eneyne compound, a preparation method and an application thereof, which are used for widening the variety of the 1, 4-eneyne compound.
The specific technical scheme is as follows:
the invention provides a 1, 4-eneyne compound which has a structure shown in a formula (I):
Figure GDA0002311489240000021
wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen, alkyl, benzene ring, naphthalene or heteroaromatic ring, preferably hydrogen, C1-C9 alkyl, benzene ring, naphthalene or C4-C10 heteroaromatic ring, R 4 Is hydrogen or silicon based.
Preferably, said R is 1 、R 2 And R 3 Each independently selected from hydrogen, C1-C6 alkyl, benzene ring, naphthalene, furan, thiophene, indole or pyrrole;
the R is 4 Selected from hydrogen, triisopropylsilyl, dimethyl tert-butylsilyl or cyclohexyl-containing oxysilane.
In the present invention, the 1, 4-eneyne compound is preferably of the following specific structure:
Figure GDA0002311489240000022
need to explainAt present, the allyl substitution reaction is widely applied to the key step of the complete synthesis of complex molecules with biological activity, and can be used as one of means for selectively introducing multifunctional alkynyl fragments into olefin molecules. However, the allyl substitution reaction still has the following problems and challenges to be solved: 1) Implementation of the allylic Csp directly using simple olefinic compounds, e.g. simple chain olefins 3 The functionalization reaction of-H, while avoiding an excessive pre-functionalization of the substrate, remains a great challenge; 2) The method is applicable to simple chain olefin substrates by using a simple catalytic system, can realize good regioselectivity and stereoselectivity, and still needs to be realized.
First, for Csp 3 -H bond alkynylation, current strategies focus mainly on pre-installation of strongly coordinating targeting groups into the molecule, such as 8-aminoquinoline, polyfluorophenylamino substituted amide derivatives. While the selective Csp is realized by directly using a simple and easily-transformed substrate 3 The ethynylation of the-H bond remains to be developed. It is particularly noted that the selective Csp is achieved by directly using simple linear olefins as "directing groups 3 The alkynylation of-H bonds not only has great utility (e.g. simple and efficient chemical conversion using readily convertible olefins to obtain highly functionalized molecules), but also is extremely challenging.
And direct Csp for highly selective linear olefins 3 The construction of 1, 4-enynes by alkynylation of the-H bond has yet to be developed, mainly because: 1) Can simultaneously realize allylic Csp of chain olefin 3 The development of a simple and effective catalytic system for regio-and stereoselective functionalization of the-H bond is urgently needed; 2) In particular, considering that terminal alkyne or alkynylating reagents are highly susceptible to Glaser reactions in oxidizing systems, resulting in self-coupled by-products, this side reaction also greatly limits efficient Csp 3 -an ethynylation of the H bond.
The invention also provides a preparation method of the 1, 4-eneyne compound, which comprises the following steps:
dissolving a compound shown in a formula (II) and a compound shown in a formula (III) in an inert solvent, and reacting under the action of an oxidant and a metal catalyst and under an alkaline condition to obtain a 1, 4-eneyne compound shown in a formula (I);
wherein the content of the first and second substances,
Figure GDA0002311489240000031
Figure GDA0002311489240000032
Figure GDA0002311489240000033
wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen, alkyl, benzene ring, naphthalene or heteroaromatic ring, R 4 Is hydrogen or silicon group;
wherein X = hydrogen, bromine, chlorine, iodine or
Figure GDA0002311489240000041
The metal catalyst is palladium acetate, palladium chloride, an iridium compound containing a trivalent state or a rhodium compound containing a trivalent state.
Preferably, the metal catalyst is ruthenium trichloride, dichloro (p-methylisopropyl) ruthenium (II) dimer, pentamethylcyclopentadienylrhodium chloride dimer, pentamethylcyclopentadienyltriacetonitrile-bis (hexafluoroantimonate) rhodium, or pentamethylcyclopentadienyliridium chloride dimer, more preferably pentamethylcyclopentadienyliridium chloride dimer or pentamethylcyclopentadienyltriacetonitrile-bis (hexafluoroantimonate) rhodium.
In the preparation method, the allyl Csp of the common chain olefin with regioselectivity is realized by preferably utilizing the good coordination of the trivalent iridium and the trivalent rhodium with the olefin and combining a proper oxidation system 3 -H bond alkynylation. The preparation method has the following characteristics: 1) The catalytic system is simple; 2) The reaction is not only applicable to allylaryl compounds, but also to alkyl olefins, directly with inert alkyl olefins or allylaryl compoundsCsp of a substance 3 The alkyne is selectively introduced from the H bond, so that the method has good atom economy and step economy, does not need substrate pre-functionalization, and accords with the synthesis concept of green chemistry; 3) The silicon base is used as a substituent of alkyne and can be conveniently removed, thereby obtaining terminal alkyne and functionalized alkyne; 4) The product molecule contains carbon-carbon double bonds which are easy to convert, so that the high-efficiency synthesis of the multi-functionalized alkyne is expected to be realized through the effective conversion of the carbon-carbon double bonds; 4) The conversion has excellent high regioselectivity and stereoselectivity, namely, the reaction generates an allyl organic metal cyclic intermediate in situ, and then performs regioselective alkynylation reaction at a position with smaller site resistance to obtain a 1, 4-eneyne compound with linear selectivity, wherein the Z/E ratio is more than 20.
In summary, the preparation method has wide application range to the substrate, can be simultaneously suitable for obtaining the 1, 4-eneyne compound with stereoselectivity, is easy for subsequent transformation, has good atom economy, can be applied to the later modification of molecules with biological activity, and solves the problem of the prior inert Csp to the alkyl olefin 3 Reactivity, site-selectivity, discrimination Csp of the activation of H bonds 3 H bond species (primary and secondary Csp) 3 -H bond, csp with allylic position to benzylic position, alpha position to the heteroatom 3 -H bond), and the like, and the prior need to install a targeting group or a leaving group, and the like, and provide important synthesis guidance for the rapid, efficient and high-value-added transformation of such widely-existing compounds.
In the present invention, the compound of formula (ii) is preferably of the following specific structure:
Figure GDA0002311489240000051
the compound of formula (iii) is preferably of the following specific structure:
Figure GDA0002311489240000052
the amount of the metal catalyst is 1mol% to 5mol%, more preferably 1mol% or 4mol%, of the amount of the compound represented by the formula (II).
Preferably, the reaction temperature is 40-150 ℃, and the reaction time is 8-48 h, more preferably 60 ℃ and 24h.
Preferably, the molar ratio of the compound represented by the formula (ii) to the compound represented by the formula (iii) is 1:2;
preferably, the base adjusting the basic conditions is selected from one or more of sodium acetate, cesium acetate, potassium acetate, sodium carbonate and potassium phosphate, more preferably lithium acetate and silver acetate.
Preferably, the inert solvent is selected from toluene, tetrahydrofuran, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, 1, 2-dichloroethane, ethanol or acetone, more preferably 1, 2-dichloroethane.
In the present invention, the amount of the base is (5 to 200) mol%, more preferably 100mol%, based on the amount of the compound represented by the formula (II);
the amount of the oxidizing agent is 10 to 300 mol%, more preferably 100mol%, based on the amount of the compound represented by the formula (II).
The concentration of the compound represented by the formula (II) in the inert solvent is 0.1mol/L to 3.0mol/L, preferably 0.2mol/L.
In the invention, bis (trifluoromethane sulfonyl) imide silver salt or silver hexafluoroantimonate is added before the reaction, the action of the catalyst is mainly ligand exchange with pentamethyl pentadienyl rhodium chloride, and silver chloride precipitation and a trivalent rhodium catalyst center coordinated by bis (trifluoromethane sulfonyl) imide radical or silver hexafluoroantimonate radical with poorer electrons are generated; furthermore, lewis acid is added, the Lewis acid can improve the electrophilic activity of the trivalent iridium or trivalent rhodium center of the metal catalyst, and the Lewis acid is preferably silver trifluoroacetate, so that the reaction efficiency is better promoted compared with other Lewis acids;
after the reaction is finished, before the 1, 4-eneyne compound is obtained, the method further comprises the following steps: and (3) filtering the reaction liquid obtained by the reaction with diatomite, performing rotary evaporation and concentration on 400-mesh silica gel to prepare dry powder, and separating the reaction product by adopting column chromatography. The developing solvent used for column chromatography is preferably petroleum ether and ethyl acetate, and the volume ratio is preferably 200:1 to 20:1, more preferably 200.
The invention also provides the application of the 1, 4-eneyne compound or the 1, 4-eneyne compound prepared by the preparation method in preparing medicines or materials.
According to the technical scheme, the invention has the following advantages:
the invention provides a 1, 4-eneyne compound with a structure shown in formula (I), wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen, alkyl, benzene ring, naphthalene or heteroaromatic ring, R 4 Is hydrogen or silicon based.
The 1, 4-eneyne compound provided by the invention widens the variety of the 1, 4-eneyne compound. The 1, 4-eneyne compound is a molecule containing unsaturated carbon-carbon double bonds and carbon-carbon triple bonds, contains a plurality of functional groups which can be conveniently transformed, such as silicon bases which are directly connected with carbon-carbon triple bonds of alkyne and can be conveniently removed, so that terminal alkyne can be obtained, and the compound has the potential of being efficiently transformed into complex molecules such as heterocycle and a plurality of unsaturated bonds through C-H transformation of the terminal alkyne, nucleophilic metallization reaction of the alkyne or cycloisomerization of the eneyne and the like, and can be widely applied to organic synthesis, material and medicine preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 shows the NMR of (E) - (5-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 a) provided in example 1 of the present invention 1 H, spectrogram;
FIG. 2 shows the NMR of (E) - (5-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 a) provided in example 1 of the present invention 13 C, spectrum;
FIG. 3 shows the NMR of (E) - (5- (p-methylphenyl) pent-4-ene) -1-triisopropylsilylacetylene (1 b) provided in example 2 of the present invention 1 H, spectrogram;
FIG. 4 shows NMR of (E) - (5- (p-methylphenyl) pent-4-ene) -1-triisopropylsilacetylene (1 b) provided in example 2 of the present invention 13 C, spectrum;
FIG. 5 shows NMR spectra of (E) - (5- (p-fluorophenyl) pent-4-ene) -1-triisopropylsilylacetylene (1 c) provided in example 3 of the present invention 1 H, spectrogram;
FIG. 6 shows NMR spectra of (E) - (5- (p-fluorophenyl) pent-4-ene) -1-triisopropylsilylacetylene (1 c) provided in example 3 of the present invention 13 C, spectrum;
FIG. 7 shows NMR of (E) - (5- (p-fluorophenyl) pent-4-ene) -1-triisopropylsilacetylene (1 c) provided in example 3 of the present invention 19 F, spectrum;
FIG. 8 shows the NMR of (4-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 d) provided in example 4 of the present invention 1 H, spectrogram;
FIG. 9 shows the NMR of (4-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 d) provided in example 4 of the present invention 13 C, spectrum;
FIG. 10 shows NMR of (4- (4-fluorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 e) provided in example 5 of the present invention 1 H, spectrogram;
FIG. 11 shows the NMR of (4- (4-fluorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 e) provided in example 5 of the present invention 13 C, spectrum;
FIG. 12 shows the NMR of (4- (4-fluorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 e) according to example 5 of the present invention 19 F, spectrogram;
FIG. 13 shows NMR of (4- (4-chlorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 f) provided in example 6 of the present invention 1 H, spectrogram;
FIG. 14 shows the NMR of (4- (4-chlorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 f) according to example 6 of the present invention 13 C, spectrum;
FIG. 15 shows a schematic view of a flowchart of example 7 of the present inventionNuclear magnetic resonance of (E) - (6-phenylhexyl-4-ene) -1-triisopropylsilacetylene (1 g) supplied 1 H, spectrogram;
FIG. 16 shows NMR of (E) - (6-phenylhexyl-4-ene) -1-triisopropylsilacetylene (1 g) provided in example 7 of the present invention 13 C, spectrum;
FIG. 17 shows NMR of (E) - (6-phenoxyhexyl-4-ene) -1-triisopropylsilacetylene (1 h) provided by example 8 of the present invention 1 H, spectrogram;
FIG. 18 shows NMR of (E) - (6-phenoxyhexyl-4-ene) -1-triisopropylsilacetylene (1 h) provided by example 8 of the present invention 13 And C, spectrum.
FIG. 19 shows NMR of (E) - (8-phenoxyoctyl-4-ene) -1-triisopropylsilacetylene (1 i) provided in example 9 of the present invention 1 H, spectrogram;
FIG. 20 shows NMR of (E) - (8-phenoxyoctyl-4-ene) -1-triisopropylsilacetylene (1 i) provided in example 9 of the present invention 13 And C, spectrum.
FIG. 21 shows NMR spectra of (E) - (8- (1, 1' -biphenyl) -4-oxy) oct-4-ene-1-triisopropylsilacetylene (1 j) provided in example 10 of the present invention 1 H, spectrogram;
FIG. 22 shows the NMR of (E) - (8- (1, 1' -biphenyl) -4-oxy) oct-4-ene-1-triisopropylsilaethynyl (1 j) provided in example 10 of the present invention 13 And C, spectrum.
FIG. 23 shows NMR spectra of (E) - (8-naphthoxy) oct-4-ene-1-triisopropylsilacetylene (1 k) provided in example 11 of the present invention 1 H, spectrogram;
FIG. 24 shows NMR spectra of (E) - (8-naphthoxy) oct-4-ene-1-triisopropylsilacetylene (1 k) provided in example 11 of the present invention 13 And C, spectrum.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
This example carries out the preparation of (E) - (5-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 a) having the following reaction formula:
Figure GDA0002311489240000091
under the air atmosphere, an olefin compound 2a (11.8mg, 0.1mmol) shown in the formula (II), pentamethylcyclopentadienyliridium (III) chloride dimer (3.2 mg), bis-trifluoromethanesulfonimide silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (36.0mg, 0.2mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin layer chromatography analysis, the reaction liquid is subjected to suction filtration by diatomite, is subjected to rotary evaporation and concentration by using 400-mesh silica gel to prepare dry powder, and a reaction product is separated by using a 400-mesh silica gel, 5 g of the 400-mesh silica gel, and a developing agent is added in a volume ratio of 200:1 with ethyl acetate to give 1, 4-enyne compound (1 a), 24.1mg, in 81% yield.
The nuclear magnetic resonance detection of (E) - (5-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 a) is shown in FIGS. 1 to 2, and the results are: 1 H NMR(400MHz,CDCl 3 )δ7.41-7.39(m,2H),7.35(t,J＝6.0Hz,2H),7.28-7.26(m,1H),6.81(d,J＝12.8Hz,1H),6.22(dt,J＝4.0Hz,12.4Hz,1H),3.26(dd,J＝2.0Hz,4.4Hz,1H),1.18-1.13(m,21H)； 13 C NMR(100MHz,CDCl 3 )δ137.2,131.3,128.6,127.3,126.3,124.2,105.0,83.4,23.4,18.7,11.4.
this example can be by Csp of a direct allylic compound 3 The position of the-H bond, stereoselectivity to obtain the 1, 4-eneyne compound.
Example 2
This example carries out the preparation of (E) - (5- (p-methylphenyl) pent-4-ene) -1-triisopropylsilacetylene (1 b), having the reaction formula:
Figure GDA0002311489240000092
under an air atmosphere, an olefin compound 2b (13.2 mg,0.1 mmol) represented by formula (ii), pentamethylcyclopentadienyltriacetonitrilobenzyl bis- (hexafluorotelluric acid) rhodium (8.3 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (36.0 mg,0.2 mmol) represented by formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe, the reaction is placed at 60 ℃ for 24 hours for reaction, the reaction is determined to be finished by thin layer chromatography, the reaction solution is subjected to suction filtration by diatomite and then is subjected to rotary evaporation and concentration by 400-mesh silica gel to prepare a dry powder, and then the reaction product is separated by column chromatography, 5 g of 400-mesh silica gel is used, and a developing agent is 200 to 20:1 with ethyl acetate to give 1, 4-enyne compound (1 b), 22.5mg, in 72% yield.
NMR detection of (E) - (5- (p-methylphenyl) pent-4-ene) -1-triisopropylsilacetylene (1 b) was performed as shown in FIGS. 3 to 4, and the results were: 1 H NMR(400MHz,CDCl 3 )δ7.24(d,J＝10.0Hz,3H),7.11(d,J＝8.0Hz,1H),6.72(d,J＝15.6Hz,1H),6.12(dt,J＝16.4Hz,5.2Hz,1H),3.20(dd,J＝5.2Hz,2.0Hz,2H),2.33(s,3H),1.13-1.06(m,21H)； 13 C NMR(100MHz,CDCl 3 )δ137.0,134.4,131.1,129.2,126.1,123.2,105.1,83.2,23.4,21.1,18.8,11.3.
this example enables Csp of allyl compounds 3 The position of the-H bond, and the stereoselective ethynylation reaction, the common benzyl active site is compatible in the reaction.
Example 3
This example carries out the preparation of (E) - (5- (p-fluorophenyl) pent-4-ene) -1-triisopropylsilacetylene (1 c) having the reaction formula:
Figure GDA0002311489240000101
under an air atmosphere, an olefin compound 2c (13.6 mg,0.1 mmol) represented by formula (ii), pentamethylcyclopentadienyliridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonimide) silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) were sequentially added to a reactor, a solution of an alkyne compound 3b (52.0 mg,0.2 mmol) represented by formula (III) in 1, 2-dichloroethane (1.0 mL) was injected into the reactor at 60 ℃ for 24 hours, the reaction was confirmed to be completed by thin layer chromatography, the reaction solution was suction-filtered through celite, column chromatography was performed by rotary evaporation and concentration on 400 mesh silica gel to obtain a dry powder, and the reaction product was isolated by using 400 mesh silica gel, 5 g of 400 mesh silica gel, and a developing reagent was added at a volume ratio of 1 to 20:1 with ethyl acetate to give 1, 4-enyne compound (1 c), 23.7mg, 75% yield.
Nuclear magnetic resonance examination of (E) - (5- (p-fluorophenyl) pent-4-ene) -1-triisopropylsilacetylene (1 c) was performed, referring to fig. 5 to 7, and the results were: 1 H NMR(400MHz,CDCl 3 )δ7.33-7.29(m,2H),7.02-6.97(m,2H),6.72(d,J＝16.0Hz,1H),6.10(dt,J＝16.4Hz,5.2Hz,1H),3.20(dd,J＝5.2Hz,3.6Hz,1H),1.14-1.06(m,21H)； 13 C NMR(100MHz,CDCl 3 )δ162.1,160.9,133.4,130.1,127.6,123.9,115.5,104.8,83.5,23.3,18.6,11.3. 19 F NMR(300MHz,CDCl 3 )δ-115.2。
the present embodiment can be compatible with a fluorine functional group widely used in the fields of materials, medicines, and the like.
Example 4
This example carries out the preparation of (4-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 d) having the following reaction scheme:
Figure GDA0002311489240000111
in a reactor, under an air atmosphere, an olefin compound 2d (11.8mg, 0.1mmol) represented by formula (ii), pentamethylcyclopentadienyliridium (III) chloride dimer (3.2 mg), bis-trifluoromethanesulfonimide silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg), and silver trifluoroacetate (22.0 mg) were sequentially added, a solution of the alkyne compound 3a (36.0 mg, 0.2mmol) represented by formula (III) in 1, 2-dichloroethane (1.0 mL) was injected into the reactor at 60 ℃ for 24 hours, the reaction was confirmed to be completed by thin layer chromatography, the reaction solution was suction-filtered through celite, column chromatography was performed by rotary evaporation and concentration on 400 mesh silica gel, and the reaction product was isolated, 5 g of 400 mesh silica gel, and a developing reagent was added at a volume ratio of 1 to 20:1 with ethyl acetate to give 1, 4-enyne compound (1 d), 23.5mg, in 79% yield.
The nuclear magnetic resonance detection of (4-phenylpentyl-4-ene) -1-triisopropylsilacetylene (1 d) is shown in FIGS. 8 to 9, and the results are: 1 H NMR(400MHz,CDCl 3 )δ7.45-7.42(m,3H),7.33-7.27(m,2H),5.54(d,J＝1.2Hz,1H),5.48(d,J＝1.2Hz,1H),3.46(t,J＝1.2Hz,2H),1.08-1.04(m,21H). 13 C NMR(100MHz,CDCl 3 )δ142.7,140.0,128.3,127.7,125.8,113.6,105.2,83.9,26.4,18.5,11.3.
this example realizes Csp of region selectivity for alpha-methylstyrene compounds 3 -H-linked ethynylation reaction, and terminal olefin Csp with higher activity to common 2 -H bond compatibility.
Example 5
This example illustrates the preparation of (4- (4-fluorophenyl) -4-pentene) -1-triisopropylsilaacetylene (1 e), which has the following reaction scheme:
Figure GDA0002311489240000121
under the air atmosphere, an olefin compound 2e (13.6 mg,0.1 mmol) shown in the formula (II), pentamethylcyclopentadienyliridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonimide) silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (36.0 mg, 0.2mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin layer chromatography, the reaction solution is filtered by suction through diatomite and then is subjected to rotary evaporation and concentration on 400-mesh silica gel to column chromatography to obtain dry powder, a reaction product is separated by adopting the 400-mesh silica gel, 5 g of the 400-mesh silica gel, and a developing agent is added in a volume ratio of 1 to 20:1 with ethyl acetate to give 1, 4-enyne compound (1 e), 24.0mg, in 76% yield.
NMR detection of (4- (4-fluorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 e), see FIGS. 10-12, results are: 1 H NMR(400MHz,CDCl 3 )δ7.42-7.39(m,2H),7.03-6.99(m,2H),5.48(d,J＝0.8Hz,1H),5.41(d,J＝0.8Hz,1H),3.43(s,2H),1.05-1.04(m,21H). 13 C NMR(100MHz,CDCl 3 )δ141.8,136.0,127.6,127.5,115.2,115.0,113.6,104.9,84.0,26.7,18.6,11.3. 19 F NMR(300MHz,CDCl 3 )δ-115.2.
this example realizes Csp of an alpha-methylstyrene compound 3 Regioselective alkynylation of the-H bond, and compatibility with fluorine functional groups, which are common in the field of materials and medicine.
Example 6
This example carried out the preparation of (4- (4-chlorophenyl) -4-pentene) -1-triisopropylsilaacetylene (1 f), whose reaction scheme is shown below:
Figure GDA0002311489240000131
under the air atmosphere, an olefin compound 2f (15.2 mg,0.1 mmol) shown in a formula (II), pentamethylcyclopentadienyl iridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonyl) imide silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3c (85.6 mg,0.2 mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at the temperature of 60 ℃, the reaction is determined to be finished by thin layer chromatography analysis, the reaction solution is subjected to suction filtration by diatomite, is subjected to rotary evaporation and condensation by silica gel of 400 meshes to column chromatography to separate a reaction product, 5 g of the silica gel of 400 meshes is adopted, and a developing agent is used in a volume ratio of 200:1 with ethyl acetate to give the 1, 4-enyne compound (1 f), 25.9mg, 78% yield.
In fig. 13 to 14, nuclear magnetic resonance detection of (4- (4-chlorophenyl) -4-pentene) -1-triisopropylsilacetylene (1 f) was performed, and the results were: 1 H NMR(400MHz,CDCl 3 )δ7.37(d,J＝8.4Hz,2H),7.29(d,J＝8.4Hz,2H),5.52(s,1H),5.46(s,1H),3.42(s,2H),1.05-1.04(m,21H). 13 C NMR(100MHz,CDCl 3 )δ141.7,138.4,133.5,128.4,127.2,114.2,104.8,84.2,26.5,18.6,11.2.
this example realizes the alpha-methylstyrene Csp 3 Regioselective alkynylation of the-H bond and compatibility with the aryl halides commonly used in metal catalyzed coupling reactions, shows good chemoselectivity, i.e., reaction only at the C-H bond and not the C-Cl bond.
Example 7
This example carried out the preparation of (E) - (6-ethylhexyl-4-en) -1-triisopropylsilacetylene (1 g), whose reaction formula is shown below:
Figure GDA0002311489240000141
under the air atmosphere, 2g (13.2mg, 0.1mmol) of an olefin compound shown in a formula (II), 3.2mg of pentamethylcyclopentadienyl iridium (III) chloride dimer, 5.8mg of bis (trifluoromethanesulfonyl) imide silver salt, 6.6mg of lithium acetate, 16.7mg of silver acetate and 22.0mg of silver trifluoroacetate are sequentially added into a reactor, a solution of an alkyne compound 3a (78mg, 0.3mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin-layer chromatography analysis, the reaction solution is subjected to suction filtration by diatomite, is subjected to rotary evaporation and concentration by 400-mesh silica gel to prepare dry powder, and then, the reaction product is separated by column chromatography, 5 g of 400-mesh silica gel is used, and a developing agent is a volume ratio of 200:1 with ethyl acetate to give 1, 4-enyne compound (1 g), 21.5mg, 69% yield.
Nuclear magnetic resonance examination was performed on (E) - (6-phenylhexyl-4-ene) -1-triisopropylsilacetylene (1 g), as shown in FIGS. 15 to 16, with the results: 1 H NMR(400MHz,CDCl 3 )δ7.30-7.25(m,3H),7.20-7.17(m,2H),5.97-5.89(m,1H),5.49(dt,J＝5.2Hz,15.2Hz,1H),3.38(d,J＝6.8Hz,2H),3.00(dd,J＝1.2Hz,4.2Hz,2H),1.10-1.02(m,21H). 13 C NMR(100MHz,CDCl 3 )δ140.4,130.7,128.5,128.3,125.9,125.6,105.8,82.3,38.5,23.0,18.6,11.3.
this example realizes the positional, stereoselective Csp of 4-phenylbutene 3 The alkynylation reaction of the-H bond not only realizes the non-allylbenzene long-chain olefin substrate which is difficult to realize in the common allyl C-H bond activation reaction, but also keeps the compatibility of the reaction to a benzyl active site.
Example 8
This example carried out the preparation of (E) - (6-phenoxyhexyl-4-ene) -1-triisopropylsilacetylene (1 h), which has the following reaction scheme:
Figure GDA0002311489240000151
under an air atmosphere, an olefin compound represented by formula (ii) 2h (14.8mg, 0.1mmol), pentamethylcyclopentadienyliridium (III) chloride dimer (3.2 mg), bis-trifluoromethanesulfonimide silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg), and silver trifluoroacetate (22.0 mg) were sequentially added to a reactor, a solution of an alkyne compound 3b represented by formula (III) (52.0 mg, 0.2mmol) in 1, 2-dichloroethane (1.0 mL) was injected into the reactor at 60 ℃ for 24h, the reaction was confirmed to be completed by thin layer chromatography, the reaction solution was suction-filtered through celite, column chromatography was performed on 400 mesh silica gel by rotary evaporation to obtain a dry powder, and the reaction product was isolated by using 5 g of 400 mesh silica gel, a developing solvent was added in a volume ratio of 1 to 20:1 with ethyl acetate to give the 1, 4-enyne compound (1 h), 23.9mg, 73% yield.
The nuclear magnetic resonance detection of (E) - (6-phenoxyhexyl-4-ene) -1-triisopropylsilacetylene (1 h) is shown in FIGS. 17 to 18, and the results are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.31-7.28(m,2H),6.97-6.93(m,2H),6.11-6.05(m,1H),5.89-5.84(m,1H),4.57-4.56(m,2H),3.12-3.10(m,2H),1.10-1.08(m,21H). 13 C NMR(100MHz,CDCl 3 )δ158.9,134.5,129.4,120.7,114.7,114.6,104.7,83.1,33.7,23.0,18.6,11.3.
this example realizes the regio-stereoselective Csp of 4-phenylether butene 3 The alkynylation reaction of the-H bond not only realizes the non-allylbenzene long-chain olefin which is difficult to realize by the conventional methodSubstrate, and the reaction is compatible with the alpha active site of the ether substrate.
Example 9
This example carried out the preparation of (E) - (8-phenoxyoctyl-4-ene) -1-triisopropylsilacetylene (1 i), whose reaction formula is shown below:
Figure GDA0002311489240000152
under the air atmosphere, an olefin compound 2i (17.6 mg,0.1 mmol) shown in a formula (II), pentamethylcyclopentadienyl iridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonylimide) silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (36.0 mg, 0.2mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin layer chromatography analysis, the reaction solution is subjected to suction filtration by diatomite, is subjected to rotary evaporation and concentration by silica gel 400 meshes to column chromatography to obtain a dry powder, and a reaction product is separated by using the 400-mesh silica gel, 5 g of the developing agent is used in a volume ratio of 200:1 with ethyl acetate to give 1, 4-enyne compound (1 i), 29.2mg, in 82% yield.
The nuclear magnetic resonance detection of (E) - (8-phenoxyoctyl-4-ene) -1-triisopropylsilacetylene (1 i) is shown in fig. 17 to 18, and the results are: 1 H NMR(400MHz,CDCl 3 )δ7.32-7.29(m,2H),6.96(t,J＝6.4Hz,1H),6.92(d,J＝6.4Hz,2H),5.86-5.80(m,1H),5.53-5.48(m,1H),3.99(t,J＝5.2Hz,2H),3.03-3.01(m,2H),2.26(dd,J＝5.6Hz,10.8Hz,2H),1.93-1.87(m,2H),1.12-1.08(m,21H). 13 C NMR(100MHz,CDCl 3 )δ159.0,130.9,129.4,124.9,120.5,114.5,105.9,82.3,67.0,28.9,28.6,18.6,11.3.
this example realizes allylic Csp for long chain terminal olefins 3 -an alkynylation of the H-bond, which conversion has good regioselectivity, e.g. alpha to the oxygen atom and carbon-hydrogen bonding of the terminal olefin do not occur, and the reaction gives a stereoselective alkynyl-containing trans-olefin product.
Example 10
This example carries out the preparation of (E) - (8- (1, 1' -biphenyl) -4-oxy) oct-4-ene-1-triisopropylsilacetylene (1 j), the reaction formula of which is shown below:
Figure GDA0002311489240000161
under the air atmosphere, an olefin compound 2j (25.2 mg,0.1 mmol) shown in the formula (II), pentamethylcyclopentadienyl iridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonylimide) silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (54.0 mg,0.3 mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin layer chromatography, the reaction solution is subjected to suction filtration by diatomite, is subjected to rotary evaporation and concentration by silica gel 400 meshes to prepare dry powder, and a reaction product is separated by a developing agent, 5 g of the silica gel 400 meshes is used, and the volume ratio of the developing agent is 200:1 with ethyl acetate to give 1, 4-enyne compound (1 j), 25.9mg, 60% yield.
Nuclear magnetic resonance detection of (E) - (8- (1, 1' -biphenyl) -4-oxy) oct-4-ene-1-triisopropylsilacetylene (1 j) was performed, as shown in fig. 17 to 18, and the results were: 1 H NMR(400MHz,CDCl 3 )δ7.57(dd,J＝0.8Hz,6.4Hz,2H),7.54(dd,J＝0.8Hz,6.4Hz,2H),7.44(t,J＝6.4Hz,3H),7.32(t,J＝6.0Hz,3H),6.99(d,J＝6.8Hz,2H),5.86-5.80(m,1H),5.54-5.49(m,1H),4.03(t,J＝5.2Hz,2H),3.02((dd,J＝1.2Hz,4.0Hz,2H),2.27(dd,J＝5.6Hz,11.2Hz,2H),1.94-1.89(m,2H),1.11-1.08(m,21H). 13 C NMR(100MHz,CDCl 3 )δ158.6,140.9,133.6,130.9,128.7,126.6,124.9,114.8,105.9,67.2,28.9,28.6,18.7,11.3.
this example realizes allylic Csp for long chain terminal olefins containing biaryl substrates 3 -an ethynylation of the H bond, the conversion having good regioselectivity and stereoselectivity.
Example 11
This example carried out the preparation of (E) - (8-naphthoxy) oct-4-ene-1-triisopropylsilacetylene (1 k) having the reaction formula:
Figure GDA0002311489240000171
under the air atmosphere, an olefin compound 2k (22.6 mg,0.1 mmol) shown in a formula (II), pentamethylcyclopentadienyl iridium (III) chloride dimer (3.2 mg), bis (trifluoromethanesulfonylimide) silver salt (5.8 mg), lithium acetate (6.6 mg), silver acetate (16.7 mg) and silver trifluoroacetate (22.0 mg) are sequentially added into a reactor, a solution of an alkyne compound 3a (54.0 mg,0.3 mmol) shown in the formula (III) and 1, 2-dichloroethane (1.0 mL) is injected into the reactor by a syringe to react for 24 hours at 60 ℃, the reaction is determined to be finished by thin layer chromatography analysis, the reaction liquid is filtered by suction through diatomite, is subjected to rotary evaporation and concentration on silica gel with 400 meshes to prepare dry powder, and then a reaction product is separated by adopting a 400-mesh silica gel with the volume ratio of 5 g, and a developing agent is 200:1 with ethyl acetate to give 1, 4-enyne compound (1 k), 31.7mg, in 78% yield.
The nuclear magnetic resonance examination of (E) - (8-naphthoxy) oct-4-ene-1-triisopropylsilylacetylene (1 k) is shown in FIGS. 17 to 18, and the results are: 1 H NMR(400MHz,CDCl 3 )δ8.34-8.32(m,2H),7.84-7.82(m,1H),7.53-7.50(m,2H),7.45(d,J＝6.4Hz,1H),7.40(t,J＝6.0Hz,1H),6.83(d,J＝6.0Hz,1H),5.92-5.86(m,1H),5.57-5.52(m,1H),4.18(t,J＝4.8Hz,2H),3.05-3.04(m,2H),2.39(dd,J＝6.0Hz,7.2Hz,2H),2.08-2.04(m,2H),1.12-1.11(m,21H). 13 C NMR(100MHz,CDCl 3 )δ154.8,134.5,131.0,125.9,12.9,127.4,125.9,125.8,124.9,122.1,120.0,105.9,104.6,82.4,67.2,29.0,28.9,18.7,11.3.
this example realizes allylic Csp of a Long chain terminal olefin containing a naphthalene Ring 3 -an ethynylation of the H bond, the conversion having good regioselectivity and stereoselectivity.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (5)

1. A preparation method of a 1, 4-eneyne compound is characterized by comprising the following steps:
dissolving a compound shown in a formula (II) and a compound shown in a formula (III) in an inert solvent, and reacting under the action of an oxidant, bis (trifluoromethane) sulfimide silver salt and a metal catalyst and under an alkaline condition to obtain a 1, 4-eneyne compound shown in a formula (I);
wherein the content of the first and second substances,
Figure FDA0003964152870000011
Figure FDA0003964152870000012
wherein X = hydrogen, bromine, chlorine, iodine or
Figure FDA0003964152870000013
Wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen, alkyl, phenyl, naphthyl, furyl, thienyl, indolyl or pyrrolyl;
the R is 4 Selected from hydrogen, triisopropylsilyl or dimethyl tert-butylsilyl;
the metal catalyst is pentamethyl cyclopentadiene iridium chloride dimer;
the oxidant is silver trifluoroacetate.
2. The method for preparing the compound of claim 1, wherein the reaction temperature is 40 ℃ to 150 ℃;
the reaction time is 8-48 h.
3. The production method according to claim 1, wherein the molar ratio of the compound represented by the formula (ii) to the compound represented by the formula (iii) is 1;
the dosage of the metal catalyst is 1-5 mol% of the dosage of the compound shown in the formula (II).
4. The method of claim 1, wherein the base for adjusting the basic condition is selected from one or more of sodium acetate, cesium acetate, potassium acetate, sodium carbonate, and potassium phosphate.
5. The method according to claim 1, wherein the inert solvent is selected from the group consisting of toluene, tetrahydrofuran, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, 1, 2-dichloroethane, ethanol and acetone.
CN201910829333.8A 2019-09-03 2019-09-03 1, 4-eneyne compound and preparation method and application thereof Active CN111320646B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910829333.8A CN111320646B (en) 2019-09-03 2019-09-03 1, 4-eneyne compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910829333.8A CN111320646B (en) 2019-09-03 2019-09-03 1, 4-eneyne compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111320646A CN111320646A (en) 2020-06-23
CN111320646B true CN111320646B (en) 2023-02-10

Family

ID=71172479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910829333.8A Active CN111320646B (en) 2019-09-03 2019-09-03 1, 4-eneyne compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111320646B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105272997A (en) * 2014-07-24 2016-01-27 中国科学院上海有机化学研究所 Difluoropropargyl-containing compound, preparation method and applications thereof
CN109704926A (en) * 2019-01-29 2019-05-03 南京工业大学 Anticancer activity molecular skeleton 1,4- enyne compounds and the preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105272997A (en) * 2014-07-24 2016-01-27 中国科学院上海有机化学研究所 Difluoropropargyl-containing compound, preparation method and applications thereof
CN109704926A (en) * 2019-01-29 2019-05-03 南京工业大学 Anticancer activity molecular skeleton 1,4- enyne compounds and the preparation method and application thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A Pd(0)-Catalyzed Direct Dehydrative Coupling of Terminal Alkynes with Allylic Alcohols To Access 1,4-Enynes;Yang-Xiong Li 等;《J. Am. Chem. Soc.》;20131231;第135卷;第12536-12539页 *
Binding Two C2 Units to an Electron-Rich Transition-Metal Center: The Interplay of Alkyne(alkynyl), Bisalkynyl(hydrido), Alkynyl(vinylidene), Alkynyl(allene), Alkynyl(olefin), and Alkynyl(enyne) Rhodium Complexes;Martin Schafer 等;《Organometallics》;20041231;第23卷;第5713-5728页 *
Chemo-and regioselective reductive deoxygenation of 1-en-4-yn-ols into 1,4-enynes through FeF3 and TfOH co-catalysis;Zonglian Yang 等;《Chem. Commun.》;20161231;第52卷;第5936-5939页 *
Regioselective C-H Bond Alkynylation of Carbonyl Compounds through Ir(III) Catalysis;Xianwei Li 等;《J. Org. Chem.》;20171231;第82卷;第13003-13011页 *
Toward the synthesis of amphidinolide P: optimization of a model ene-yne metathesis fragment coupling;Edgars Jecs 等;《Tetrahedron Letters》;20141231;第55卷;第4933-4937页 *
Yang-Xiong Li 等.A Pd(0)-Catalyzed Direct Dehydrative Coupling of Terminal Alkynes with Allylic Alcohols To Access 1,4-Enynes.《J. Am. Chem. Soc.》.2013,第135卷第12536-12539页. *
Zonglian Yang 等.Chemo-and regioselective reductive deoxygenation of 1-en-4-yn-ols into 1,4-enynes through FeF3 and TfOH co-catalysis.《Chem. Commun.》.2016,第52卷第5936-5939页. *

Also Published As

Publication number Publication date
CN111320646A (en) 2020-06-23

Similar Documents

Publication Publication Date Title
CN110156660B (en) Isoindoline derivative and preparation method thereof
Han et al. Cobalt-catalyzed diastereoselective difluoroalkylation/Giese addition domino reactions
Wang et al. Chiral CpxRh complexes for C–H functionalization reactions
CN113563370B (en) Preparation method for preparing beta-boron-based ketone with alpha-position substituent by catalysis of chitosan loaded copper material
Cao et al. Axially chiral C2-symmetric N-heterocyclic carbene (NHC) palladium complex-catalyzed asymmetric α-hydroxylation of β-keto esters
CN115197138B (en) Preparation method of isoquinoline derivative
Fan et al. Air-Stable Half-Sandwich Iridium Complexes as Aerobic Oxidation Catalysts for Imine Synthesis
CN109535204B (en) Rhodium complex, preparation method, intermediate and application thereof
CN115108960A (en) Preparation method and application of polysubstituted indole compound
Li et al. Enantioselective Synthesis of Bicyclo [3.2. 1] octadienes via Palladium‐Catalyzed Intramolecular Alkene‐Alkyne Coupling Reaction
CN111320646B (en) 1, 4-eneyne compound and preparation method and application thereof
Li et al. Norbornene in organic synthesis
Yang et al. Rhodium‐Catalyzed Enantio‐and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes
CN110256480B (en) Alkynyl-containing nitrogen-containing heterocyclic derivative and preparation method and application thereof
CN114478362A (en) Preparation method of chiral pyridinol derivative
Barry et al. Synthesis and catalytic epoxidation activity of terpene-derived D4-symmetric metalloporphyrins
Biswas et al. Cu (i)-Catalyzed asymmetric exo-selective synthesis of substituted pyrrolidines via a 1, 3-dipolar cycloaddition reaction
Kong et al. Synthesis of spiro dienones from internal acetylene and cyclic 3-iodo enones in the presence of nickel bromide and zinc powder
CN110305156B (en) Alkyne derivative containing nitrogen-oxygen bond and preparation method and application thereof
CN110317172B (en) Azafluorenone derivative and preparation method and application thereof
CN109896970A (en) The preparation method of 2- amino -3- carbonyl indene derivative and azatropylidene analog derivative
You et al. Catalytic Enantioselective Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones and Vinyl Selenides
Gao et al. Diastereoselective Palladium-Catalyzed Conjugate Addition of Arylboronic Acids to α-Substituted Cyclic Enones
Zhan et al. Copper-catalyzed 4-HO-TEMPOH mediated phosphorylation of alkenes
CN110305157B (en) Conjugated eneyne amide derivatives, and preparation method and application thereof

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