CN117069755A - Preparation method of benzofuran chiral disilicide compound - Google Patents

Preparation method of benzofuran chiral disilicide compound Download PDF

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CN117069755A
CN117069755A CN202310982892.9A CN202310982892A CN117069755A CN 117069755 A CN117069755 A CN 117069755A CN 202310982892 A CN202310982892 A CN 202310982892A CN 117069755 A CN117069755 A CN 117069755A
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chiral
benzofuran
disilicide
palladium
preparation
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张俊良
周璐佳
张展鸣
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Suzhou Kerroli New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • 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
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a preparation method of benzofuran chiral disilicide, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps of S1, adding palladium salt and chiral ligand L into a solvent under protective atmosphere, and reacting to obtain a catalyst [ Pd ]]solution/L; s2, will

Description

Preparation method of benzofuran chiral disilicide compound
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of benzofuran chiral disilicide compounds.
Background
The chiral organosilicon compound has wide application in the fields of synthetic organic chemical materials, pharmacy, pesticides and the like, and is gradually expanded to other new fields. Transition metal catalyzed silylation is one of the very efficient methods for rapidly building bis-containing silicon compounds. Currently, a number of efficient synthetic methods have been developed. For example, in 2018, the first series Heck/silylation reaction was developed by Zhang et al (Angew. Chem. Int. Ed.2018, 3233-3237) and the synthesis of a series of bis-silylated indolones was achieved in good yields. Thereafter, similar reactions were reported by Lautens et al (org. Lett.2020, 3679-3683) in 2020, and a series of disilicide substituted chromans were synthesized in moderate to excellent yields. However, the only methods reported for the disilicide are limited to the synthesis of racemic disilicide, and the problem of asymmetric catalysis has not been solved. Although Xu Liwen et al (Asian J. Org. Chem.2018, 1403-1410) attempted to address the asymmetric synthesis of such disilicide compounds, high throughput screening also resulted in only one example of a disilylated product with moderate enantioselectivity (76% ee). Therefore, the further synthesis of benzofuran chiral disilicide with rich and diverse structures is still worthy of further exploration.
Disclosure of Invention
The invention aims to provide a preparation method of benzofuran chiral disilicide compound, which has the advantages of nontoxic, simple and easily obtained raw materials, simple and convenient operation and high enantioselectivity.
The invention aims to provide a preparation method of benzofuran chiral disilicide compounds, which comprises the following steps,
s1, adding palladium salt and chiral ligand L into a solvent under a protective atmosphere, and reacting to obtain a catalyst [ Pd ]/L solution;
s2, adding a compound with a structure shown in a formula I, a disilane compound with a structure shown in a formula II and alkali into a catalyst [ Pd ]/L ] solution shown in the formula S1, and reacting to obtain a benzofuran chiral disilicide compound shown in a structure shown in a formula III;
wherein the structural formulas of the formulas I, II and III are as follows,
R 1 selected from hydrogen, halogen, aryl, C 1-6 Alkyl or C 1-30 An alkoxy group;
R 2 selected from C 1-6 Alkyl, phenyl, 1-naphthyl, 2-naphthyl or heteroaryl.
The specific reaction route is as follows,
in one embodiment of the present invention, the disilane compound of the structure of formula II refers to a compound that is C between silicon and silicon 0 Or C 4-5 And a linked disilane compound.
In one embodiment of the present invention, in S1, the chiral ligand has the structure shown in formula IV,
wherein R is 3 Independently selected from hydrogen, aryl, C 1-6 Alkyl, C 1-6 An alkoxy group or a plurality of substituents are bonded to form a ring;
R 4 selected from C 1-6 Alkyl, substituted or unsubstituted phenyl, 1-naphthyl, 2-naphthyl or heteroaryl, said substituted phenyl having a number of substituents ranging from 1 to 5, said substituted phenyl substituents being selected from C 1-8 Alkyl, C 1-6 Alkoxy, halogen, trifluoromethyl or a plurality of substituents are bonded to form a ring;
R 5 selected from hydrogen, deuterium or C 1-6 An alkyl group;
R 6 selected from C 1-10 Alkyl or phenyl.
In one embodiment of the invention, the chiral ligand L is selected from the group consisting of,
in one embodiment of the present invention, in S1, the palladium salt is selected from one or more of tris (dibenzylideneacetone) dipalladium chloroform adduct, tris (dibenzylideneacetone) dipalladium, palladium chloride, palladium acetate, palladium trifluoroacetate, bis (dibenzylideneacetone) palladium, allyl palladium chloride, palladium acetate, palladium trifluoroacetate, tetraacetonitrile palladium tetrafluoroborate, bis (acetylacetonato) palladium, (1, 5-cyclooctadiene) palladium dichloride, bis (acetonitrile) palladium chloride, and bis (2-methallyl) palladium chloride.
In one embodiment of the present invention, in S1, the solvent is selected from one or more of tetrahydrofuran, toluene, diethyl ether, ethyl acetate, N-hexane, dichloromethane, methanol, methyl t-butyl ether and N, N-dimethylformamide.
In one embodiment of the invention, in S1, the temperature of the reaction is 15 ℃ to 50 ℃; the reaction time is 0.5h-1.5h.
In one embodiment of the present invention, in S1, the gas of the protective atmosphere is argon.
In one embodiment of the present invention, in S2, the base is selected from one or more of triethylamine, diisopropylethylamine, potassium carbonate, cesium carbonate, lithium carbonate, rubidium carbonate, potassium phosphate, sodium carbonate, sodium bicarbonate, sodium hydroxide, and sodium tert-butoxide.
In one embodiment of the invention, in S2, the temperature of the reaction is 60 ℃ to 120 ℃; the reaction time is 12-48 h.
In one embodiment of the present invention, the molar ratio of palladium salt, chiral ligand L, compound of formula I, compound of formula II, and base is 0.01-0.1:0.01-0.5:1:4.0-6.0:0.5-5.0.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) According to the preparation method, the catalyst [ Pd ]/L ] composed of the chiral tert-butylsulfinamide ligand and the palladium salt is adopted, so that the limitation of the existing method is broken through, the intramolecular asymmetric silicon-based reaction of the o-iodo-alkenyl ether compound is realized, the benzofuran chiral disilicide compound is obtained, and the preparation method has the characteristics of non-toxic, simple and easily obtained raw materials, simplicity and convenience in operation, high enantioselectivity and the like, can be used for carrying out structural modification on the medicinal molecular derivative, and has a wide application prospect.
(2) Compared with the traditional silicon-based reaction, the preparation method provided by the invention has the advantages that the raw materials are nontoxic, simple and easily available, and the atomic economy is very good; the method is simple to operate, has wide substrate universality, and can complete the synthesis of the benzofuran chiral disilicide compound with the structure shown in the formula III in one step.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
(1) In the present invention, abbreviations represent the meanings shown in table 1, unless otherwise indicated:
TABLE 1
(2) In the present invention, the preparation of chiral ligand L is carried out by the chinese patent with reference to patent application nos. 201910831293.0, 201510107308.0 and 201310671902.3, and the preparation method of chiral ligand L is as follows:
into a dry 500mL three-port reaction flask, imine (40 mmol) was added, 250mL of redistilled tetrahydrofuran was added under argon atmosphere, and after the solution temperature was completely stabilized at-48℃or-78℃80mL of a substituent magnesium bromide reagent or a substituent lithium reagent was added in a constant pressure funnel (80.0 mmol), and the dropping rate was controlled to 2 drops per second. After 2h of reaction, the refrigeration was turned off overnight and stirring was continued at room temperature for 2h. After completion of the TLC detection reaction, 100mL of saturated ammonium chloride solution or iodide (80.0 mmol) was added for quenching. Transfer to a 1L separating funnel, extract three times with 100mL ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, and concentrate. The crude product is dissolved by 56mL of acetone, 40mL of distilled water is dropwise added at the temperature of minus 10 ℃, cooled and crystallized for 3h, and the chiral ligand L is obtained after drying.
(3) In the present invention, chiral ligand L used in examples is for convenience of description * Respectively referred to as L1-L20, and the corresponding structural formulas are as follows:
(4) In the present invention, for convenience of description, chiral ligand L used in comparative example * Respectively referred to as L21-L28, and the corresponding structural formulas are as follows:
(5) In the invention, the preparation method of the benzofuran chiral disilicide compound comprises the following steps:
s1: chiral ligand L * (0.09 mmol), palladium salt (0.03 mmol), and a solvent (1.5 mL) were added under argon atmosphere to the reaction flask, and the mixture was stirred at 25℃for 1 hour to obtain a catalyst [ Pd ]]/L * A solution.
S2: catalyst [ Pd ] prepared as above]/L * 1-iodo-2- ((2-phenylallyl) oxy) benzene of formula I (100.8 mg,0.3 mmol), formula IIThe resultant hexamethyldisilane (1.8 mmol) and a base (0.6 mmol) were heated to 100℃and reacted for 24 hours, after which dibromomethane (0.3 mmol) was added as an internal nuclear magnetic standard after concentration, the nuclear magnetic yield was measured, and the enantioselectivity (ee value) was measured by HPLC.
(6) In the invention, the substrate suitable for the preparation method of the benzofuran chiral disilicide is expanded, and the reaction formula is as follows:
the preparation method comprises the following specific steps:
s1: chiral ligand L13 (63.0 mg,0.09 mmol), tris (dibenzylideneacetone) dipalladium chloroform adduct (Pd) 2 (dba) 3· CHCl 3 ) (15.5 mg,0.03 mmol) was added to a reaction flask and methyl tert-butyl ether was added under argon with 5% N, N-dimethylformamide: 1 (1.5 mL) and stirring at 25deg.C for 1h to obtain catalyst [ Pd ]]Mixed solution of methyl tertiary butyl ether of L13 and N, N-dimethylformamide;
s2: the catalyst prepared above was added with a mixed solution of [ Pd ]/L13 methyl tert-butyl ether and N, N-dimethylformamide in order with an o-iodophenol-derived alkenyl ether compound of the structure of formula I (0.3 mmol), a disilane compound of the structure of formula II (1.2 mmol) and potassium carbonate (82.9 mg,0.6 mmol), and the mixture was heated to 100℃and reacted for 24 hours, followed by column separation to obtain the objective product of the structure of formula III.
Example 1
A process for the preparation of (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane comprising the steps of:
s1: chiral ligand L13 (14.4 mg,0.0225 mmol), tris (dibenzylideneacetone) dipalladium chloroform adduct (Pd 2 (dba) 3· CHCl 3 ) (15.5 mg,0.03 mmol) was added to the flask and methyl tert-butyl ether was added under argon with 5% N, N-dimethylformamide: 1 (1.5 mL) and stirring at 25deg.C for 1h to obtain catalyst [ Pd ]]Methyl tert-butyl ether of L13 with NA mixed solution of N-dimethylformamide;
s2: to a mixed solution of methyl tert-butyl ether and N, N-dimethylformamide of the catalyst [ Pd ]/L13 prepared above was added successively 1-iodo-2- ((2-phenylallyl) oxy) benzene (100.8 mg,0.3 mmol), hexamethyldisilane (175.7 mg,1.2 mmol), potassium carbonate (82.9 mg,0.6 mmol), and the mixture was heated to 100℃to react for 24 hours, followed by column separation to obtain (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane in a yield of 96% and an ee value of 92%.
White solid; [ alpha ]] D 20 ＝-132.0(c＝0.40,CHCl 3 ). 1 H NMR(400MHz,CDCl 3 )δ
7.81-7.73(m,1H),7.26-7.12(m,4H),7.08-7.02(m,1H),7.02-6.95(m,1H),6.88(d,J＝8.0Hz,1H),4.80(d,J＝8.8Hz,1H),4.64(d,J＝8.8Hz,1H),2.00(d,J＝14.8Hz,1H),1.51(d,J＝14.8Hz,1H),0.46(s,9H),-0.14(s,9H).MS(EI):m/z(％)＝354(M + 10.31), 73 (100) ee value: 92%, determined by HPLC (ChiralpakAD-H+AD-3, hexanes: 2-Propanol=99.5:0.5; flow rate 0.5mL/min;25 ℃ C.; 220 nm), t r (major)＝15.5min,t r (minor)＝14.4min.
Examples 2 to 21
A process for the preparation of (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane, the specific preparation procedure being described in example 1, the preparation of (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane as an adjunct reagent, the yields measured by nuclear magnetism and the enantioselectivities (ee values) are shown in table 2:
TABLE 2
As can be seen from Table 2, L13 is the most preferred chiral ligand, the tris (dibenzylideneacetone) dipalladium chloroform adduct is the most preferred palladium salt, potassium carbonate is the most preferred base, and methyl t-butyl ether is the most preferred mixed solvent with N, N-dimethylformamide (5:1).
Examples 22 to 37
The substrate suitable for the preparation method of the benzofuran chiral disilicide is expanded, and the preparation method comprises the following specific steps:
s1: chiral ligand L13 (14.4 mg,0.0225 mmol), tris (dibenzylideneacetone) dipalladium chloroform adduct (Pd 2 (dba) 3· CHCl 3 ) (15.5 mg,0.03 mmol) was added to the flask and methyl tert-butyl ether was added under argon with 5% N, N-dimethylformamide: 1 (1.5 mL) and stirring at 25deg.C for 1h to obtain catalyst [ Pd ]]Mixed solution of methyl tertiary butyl ether of L13 and N, N-dimethylformamide;
s2: to the mixed solution of methyl tert-butyl ether and N, N-dimethylformamide of the catalyst [ Pd ]/L13 prepared above were added sequentially an o-iodophenol-derived alkenyl ether compound (0.3 mmol), a disilane compound (1.2 mmol) and potassium carbonate (82.9 mg,0.6 mmol), and after the reaction was carried out at 100℃for 24 hours, the target product represented by the formula III was obtained by column separation, and the specific structure, yield, ee value and data characterization of the compound were as shown in Table 3:
TABLE 3 Table 3
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As can be seen from Table 3, the process is very versatile for both compounds of the formula I and disilane compounds of the formula II, which are substituted in various classes.
Comparative examples 1 to 8
A process for the preparation of (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane, the specific preparation procedure being described in example 1, the preparation of (S) -trimethyl (5-methyl-2- (3- ((trimethylsilyl) methyl) -2, 3-dihydro-benzofuran-3-yl) phenyl) silane as an adjunct reagent, the yields measured by nuclear magnetism and the enantioselectivities (ee values) are shown in table 4:
TABLE 4 Table 4
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As can be seen from table 4, the known chiral ligands L25, L26, L27 and L28 cannot catalyze this reaction, and no compound of formula III is obtained. Although the compounds of formula III can be obtained in low to moderate yields when using the well-known chiral ligands L21, L22, L23 and L24, very low ee is achieved, and it can be seen that the schemes of the examples of the invention achieve very good results.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. A preparation method of benzofuran chiral disilicide compounds is characterized by comprising the following steps,
s1, adding palladium salt and chiral ligand L into a solvent under a protective atmosphere, and reacting to obtain a catalyst [ Pd ]/L solution;
s2, adding a compound with a structure shown in a formula I, a disilane compound with a structure shown in a formula II and alkali into a catalyst [ Pd ]/L ] solution shown in the formula S1, and reacting to obtain a benzofuran chiral disilicide compound shown in a structure shown in a formula III;
wherein the structural formulas of the formulas I, II and III are as follows,
R 1 selected from hydrogen, halogen, aryl, C 1-6 Alkyl or C 1-30 An alkoxy group;
R 2 selected from C 1-6 Alkyl, phenyl, 1-naphthyl, 2-naphthyl or heteroaryl.
2. The method for preparing benzofuran chiral disilicide according to claim 1, wherein in S1, the chiral ligand L has a structure shown in formula IV,
wherein R is 3 Independently selected from hydrogen, aryl, C 1-6 Alkyl, C 1-6 An alkoxy group or a plurality of substituents are bonded to form a ring;
R 4 selected from C 1-6 Alkyl, substituted or unsubstituted phenyl, 1-naphthyl, 2-naphthyl or heteroaryl, said substituted phenyl having a number of substituents ranging from 1 to 5, said substituted phenyl substituents being selected from C 1-8 Alkyl, C 1-6 Bonding between alkoxy, halogen, trifluoromethyl or substituentsForming a ring;
R 5 selected from hydrogen, deuterium or C 1-6 An alkyl group;
R 6 selected from C 1-10 Alkyl or phenyl.
3. The process for the preparation of benzofuran chiral disilicide according to claim 2, wherein the chiral ligand L is selected from the group consisting of,
4. the method for producing a benzofuran chiral disilicide according to claim 1, wherein in S1, the palladium salt is selected from one or more of tris (dibenzylideneacetone) dipalladium chloroform adduct, tris (dibenzylideneacetone) dipalladium, palladium chloride, palladium acetate, palladium trifluoroacetate, bis (dibenzylideneacetone) palladium, allyl palladium chloride, palladium acetate, palladium trifluoroacetate, tetraacetonitrile palladium tetrafluoroborate, bis (acetylacetonate) palladium, (1, 5-cyclooctadiene) palladium dichloride, bis (acetonitrile) palladium chloride and bis (2-methallyl) palladium chloride.
5. The method for producing a benzofuran chiral disilicide according to claim 1, wherein in S1, the solvent is selected from one or more of tetrahydrofuran, toluene, diethyl ether, ethyl acetate, N-hexane, dichloromethane, methanol, methyl t-butyl ether and N, N-dimethylformamide.
6. The process for the preparation of a benzofuran chiral disilicide according to claim 1, wherein in S1 the temperature of the reaction is 15 ℃ to 50 ℃; the reaction time is 0.5h-1.5h.
7. The method for producing a benzofuran chiral disilicide according to claim 1, wherein in S1, the gas of the protective atmosphere is argon.
8. The method for producing a benzofuran chiral disilicide according to claim 1, wherein in S2, the base is selected from one or more of triethylamine, diisopropylethylamine, potassium carbonate, cesium carbonate, lithium carbonate, rubidium carbonate, potassium phosphate, sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium tert-butoxide.
9. The process for the preparation of a benzofuran chiral disilicide according to claim 1, wherein in S2 the temperature of the reaction is from 60 ℃ to 120 ℃; the reaction time is 12-48 h.
10. The method for preparing a benzofuran chiral disilicide according to claim 1, wherein the molar ratio of palladium salt, chiral ligand L, compound of formula I, compound of formula II, and base is 0.01-0.1:0.01-0.5:1:4.0-6.0:0.5-5.0.
CN202310982892.9A 2023-08-07 2023-08-07 Preparation method of benzofuran chiral disilicide compound Pending CN117069755A (en)

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