CN112028919B - B (3)/B (3,6) -o-carborane alkylation method of compound - Google Patents
B (3)/B (3,6) -o-carborane alkylation method of compound Download PDFInfo
- Publication number
- CN112028919B CN112028919B CN202010844238.8A CN202010844238A CN112028919B CN 112028919 B CN112028919 B CN 112028919B CN 202010844238 A CN202010844238 A CN 202010844238A CN 112028919 B CN112028919 B CN 112028919B
- Authority
- CN
- China
- Prior art keywords
- cdcl
- nmr
- carborane
- group
- mono
- 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
Links
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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
Abstract
The invention discloses a B (3)/B (3,6) -o-carborane alkylation method of a compound, which is characterized in that the compound is derived into active amide with an N-acyl-diimide group, and the active amide is cross-coupled with o-carborane with an imine group on a cage carbon under the catalysis of an Rh catalyst. The method can realize the carborane alkylation modification of functional compounds such as medicinal active substances, fluorescent molecules and the like, and can also carry out functionalization on the B (3)/B (3,6) position of o-carborane. Compared with the traditional coupling method, the invention realizes direct B-H activation functionalization, overcomes the defects of environmental pollution, dangerous reaction conditions, yield loss in multi-step reaction and the like caused by B (3) pre-activation in the prior art, and has better solubility and functional group compatibility and better industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a B (3)/B (3,6) -o-carborane alkylation method of a compound.
Background
The carborane is polyhedral carborane molecular cluster, namely dodecahedral icosahedral dicarbo enclosed carborane (closo-C)2B10H12Hereinafter, abbreviated as "carborane"), there are three isomers, ortho carborane is widely used in luminescent materials, metal organic frameworks, nano-scale materials, electronic storage materials, liquid crystals, catalysis and other aspects due to its special properties such as three-dimensional aromaticity, large steric hindrance, multi-directional B-H and C-H bonds and non-classical interaction, and can be used as a good "mode molecule" for physical organic chemistry research. The o-carborane has very high boron content and has potential application in boron neutron capture therapy. Hosmane developed a water-soluble carbon nanotube modified with a large number of vicinal carborane groups, which utilized the properties of carbon nanotubes to highly aggregate boron-rich nested carboranes in a limited volume. The research shows that boron atoms can be enriched in blood and cancerated tissues of other organs, and the boron neutron capture therapy has very good application prospect for removing tumor tissues.
The orthocarbon borane has the characteristics of longer C-C bond, electron-withdrawing induction effect at the carbon end, electron-donating effect in different degrees at the boron end and the like, and the carborane has large steric hindrance effect and three-dimensional aromaticity, so that the distribution of electronic orbitals of HOMO and LUMO of a substituted compound can be adjusted, the whole boron cage can participate in electronic delocalization of adjacent luminous compound fragments, certain unusual regulation and control luminescence properties are displayed, and the orthocarbon borane can be applied to the regulation and control of the fluorescence activity property in a fluorescent molecule. For example, Lee research room in Korea and Yan hong professor group of subjects at Nanjing university summarize the rules of carborane group for fluorescence red shift, blue shift and quenching, and a part of molecules for regulating and controlling luminescence of carborane are found to be sensitive to dielectric constant of solvent, so that the carborane is applied to two-photon absorption and hypoxic imaging research of tumor cells.
Because two C-H of unsubstituted ortho-carborane molecules have strong acidity, and H of ten inert B-H bonds shows partial negative hydrogen property, the whole molecule has hydrophobicity and can form B-H … H-X hydrogen bonds, and the carborane is a very potential substituent group for drug molecules. Since 2010, Kagechika,
And
sufficient evidence for the presence of B-H-X (X ═ O, N, C) di-hydrogen bonds between the carborane groups and the proteins, respectively, was found. In 2015, Hawthorne and coworkers designed boron polycarbophil, which is the first local anesthetic tethered by B (3) -o-carborane group and the only report of a biologically active ortho-carborane derivative with a B (3) site linked to an organic structure.
To date, most carborane materials are compounds derivatized at the C-terminus. This is because the selective catalysis of the B-terminal has been very limited in the past, which also greatly affects the flexible selective attachment of carborane as a specific functional group to drug fragments and luminescent molecules. In the prior art, most carborane B (3) site selective substitution reactions require starting from a B (3) pre-functionalized precursor. Such a strategy requires multiple steps and presents a danger(e.g., use of equivalent virulent TlOAc reagent, use of liquid ammonia, strong oxidizer KMnO4Neutralization of the remaining Na, THF at 110 ℃ for blocking reaction), moisture-sensitive reaction conditions (BI)3、PhBCl2The use of metallic Na) and low tolerance to functional groups.
Xu et al disclose an in-Situ Pd-NHC Catalytic System for regioselective Arylation of adjacent Carborane B (3,6) -H bond, synthesizing a series of symmetric and asymmetric 3, 6-diaryl-o-Carboranes (Old keys of The Lock in Carborane: The in Situ NHC-Palladium catalyst System for Selective aryl of B (3,6) -H Bonds of o-Carboranes via B-H activation. org. Lett.2019,21,9276 + 9279) with active groups. This method uses an excess of oxidant and the substrate type is limited by electron deficient substituents.
Tang et al, using a nucleophilic substitution strategy, propose a novel regioselective nucleophilic cage B-H substitution method for vicinal carboranes, leading to a series of dialkylated B (3,6) and alkylated/arylated vicinal carboranes. (Regioselective Nuclear amplification/Alkylation of B-H Bonds in o-carbohydrates: An Alternative Method for Selective vessel Boron functioning, J.Am.chem.Soc.2018, 140, 16423-16427).
However, the use of the Grignard reagent greatly limits the compatibility of functional groups (e.g., ester groups, amide groups, carbonyl groups, etc.) that are sensitive to the Grignard reagent. The reaction substrates available are limited. Lower reaction temperatures are detrimental to the dissolution of larger organic compounds, and thus it is difficult to achieve late stage boronation of complex organic compounds. In addition, the method must carry out reaction only by methyl and alkynyl which cannot be removed by C-terminal modification, otherwise, the reaction cannot be carried out.
At present, willWith B (3) -o-carboranyl bound to C (sp)2)/C(sp3) The organic substances present a great challenge because: (1) b (3) is the most electron deficient site in the cage structure. The electron enrichment order of the boron sites is: b (9,12)>B(8,10)>B(4,5,7,11)>B (3, 6). Thus, B (3) is easily attacked by nucleophiles, causing the boronization reaction to be a very serious disturbance in the chemical conversion of all compounds containing a closed-carboranyl group. Thus, many bases and even certain polar aprotic solvents cannot be used in order to avoid the deboronation reaction. In addition, boranes are reducing and oxidizing agents should be used with caution. For metal-induced electrophilic substitution, B (3) is more inert. (2) In most cases, it is necessary to pass through the carbon atom of the closure cage (i.e.C)cageReplacement of the H atom of-H with alkyl, aryl) to achieve selective B-H functionalization. To address the reactivity problem of electron deficient B (3) and B (4) ends, it is common to mount a Directing Group (DGs) at the carbon end of the carborane to force the reaction to occur at either B (3) or B (4). The existing studies show that C existscageIn the case of-H, mixtures of inseparable substitutions of B (3) and B (4) result. Furthermore, in most directed B-H activation reactions, which actually undergo electrophilic reaction mechanisms, coupled with the steric hindrance of the C-terminal placing group, the B (4) site is functionalized instead of the B (3) site. (3) The substrate applicability is narrow and at least one evaluation of the applicability to a wide range of synthetic chemistry is lacking. Although there are already some B (3)/B (4) -C (sp)2) Some reports have been coupled, but the generality of these methods has not been fully evaluated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a B (3)/B (3,6) -o-carborane alkylation method, which uses o-carborane with imine mounted on cage carbon and sp derivative2Or sp3The active amide of hybridized carboxylic acid (as aryl source, alkenyl source and alkyl source) is catalyzed by Rh (I) to realize B (3) -o-carbon alkyl and C (sp)2)/C(sp3) Cross-coupling of (3).
The specific technical scheme of the invention is as follows:
a process for the B (3)/B (3,6) -o-carborane alkylation of compounds characterized by derivatizing the compounds into activated amides having N-acyl-imide groups, cross-coupling with an o-carborane having an imine group on a cage carbon, catalyzed by Rh catalyst.
Preferably, the Rh catalyst is selected from [ Rh (cod) Cl]2And/or Rh2(CO)4Cl2。
In the method of the present invention, the N-acyl-imide group has the following parent nucleus structure:
n is an integer of 0 to 5. When n represents 1 to 5, the parent nucleus may have one or more of the same or different substituents, such as C1-10 alkyl, C1-10 alkoxy, C1-10 ester group, halogen group and the like. Preferably, the N-acyl-imide group is a substituted or unsubstituted N-acyl-glutarimide or N-acyl-succinimide.
According to the method, the nitrogen atom on the imine group on the adjacent carborane cage carbon is substituted by aryl or heteroaryl. Further, the aryl or heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted bicyclic or tricyclic aromatic group, (e.g., naphthyl group, anthracenyl group substituted with H, C1-10 alkyl group, C1-10 alkoxy group, C1-10 ester group, halogen group, etc.) or a substituted or unsubstituted monocyclic, bicyclic or tricyclic heterocyclic aromatic group containing one or more N, O, S hetero atoms (e.g., furyl group, thienyl group, pyrrolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, pteridinyl group, acridinyl group, etc., substituted with H, C1-10 alkyl group, C1-10 alkoxy group, C1-10 ester group, halogen group, etc.). Preferably phenyl, thienyl, furyl, pyridyl and pyrimidyl which are substituted by one or more of H, methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In a specific embodiment of the invention, aryl is selected from
(Mes)。
The above-mentionedThe orthocarborane having an imine group has the following structure:
ar represents an aryl or heteroaryl group, R1Represents H or C1-C10 alkyl.
Specifically, the method is characterized by comprising the following reaction formula:
R1represents H, C1-C10 alkyl, R2，R3And represents the residue of the compound to be alkylated by B (3)/B (3,6) -o-carborane in the invention, Ar is defined as the above, and represents substituted or unsubstituted phenyl, monocyclic, bicyclic or tricyclic aromatic group or monocyclic, bicyclic or tricyclic heterocyclic aromatic group containing one or more N, O, S heteroatoms, n is an integer of 1-5, preferably n is 2 or 3.
Preferably, R2、R3Represents phenyl, biphenyl, naphthyl, pyridyl, oxazinyl, thienyl, furyl, thiazolyl, oxazolyl, imidazolyl, which is substituted at any position by one or more of H, C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 haloalkyl, C1-C8 ester, aldehyde, halogen, cyano, amine, carbonyl, amide, sulfone, sulfoxide, thio, sulfonamide, nitro, phosphonyl, trifluoromethyl, trifluoromethoxy, thifluoromethyl, alkenyl, fluoroalkyl, polyfluoroaryl, aryl, glycosyl, purinyl, pyrimidinyl, carboranyl.
In a specific example of the present invention, R2、R3Represents:
in the method, the preferable reaction temperature is 130-150 ℃, and the reaction solvent is one or more selected from toluene, o-xylene, m-xylene or p-xylene.
When carboxyl or acyl chloride or acyl bromide groups in the structure of the compound are in reaction, the compound can directly react with diimide to obtain active amide with N-acyl-diimide groups, or the compound is converted through derivatization reaction and then is connected with the carboxyl or acyl chloride or acyl bromide groups to react with the diimide.
The method of the invention also comprises the step of further converting the obtained B (3)/B (3,6) -o-carborane alkylate after the reaction is finished.
The conversion comprises one or more of removal of an imine group on an o-carborane caged carbon, stitution of a substituted carbon end of carborane, boronization of carborane or derivatization of a compound residue part, and the like.
In the method of the present invention, when an active hydrogen group is present in the compound, it is preferable that the active hydrogen group is protected with a protecting group before the reaction, and the protecting group is removed after cross-coupling with an o-carborane having an imine group on a cage carbon. The active hydrogen group is selected from one or more of hydroxyl, amino, sulfydryl, carboxyl, sulfo and sulfonamido. The protecting group may be a conventionally used protecting group such as BHT (2, 6-di-t-butyl-4-methylphenyl), Bn (benzyl), BOC (t-butyloxycarbonyl), BOM (benzyloxymethyl), Cbz (benzyloxycarbonyl), CDA (cyclohexyl-1, 2-diketal), DAN (dansyl), Fmoc (9-fluorenylmethoxycarbonyl), TBDMS (t-butyldimethylsilyl).
The invention has the advantages that:
the invention successfully introduces compound fragments into the B (3)/B (3,6) position of o-carborane by derivatizing a compound into an active amide with an N-acyl-diimide group and carrying out cross coupling with o-carborane with an imine group on a cage carbon under the catalysis of Rh (I). The method can realize the carborane alkylation modification of functional compounds such as medicinal active substances, fluorescent molecules and the like, and can also carry out functionalization on the B (3)/B (3,6) position of o-carborane.
The invention uses N-acyl-diimide active amide as the precursor of compound fragment with aryl, heteroaryl, alkenyl, primary alkyl, etc. and uses Rh (I) to perform two-step oxidation addition to the primary amido bond of B-H bond, so that no oxidant is needed in the reaction. In addition, because amine-based anions are generated in the reaction process, no additional strong alkaline substances are needed for the reaction. This allows the carborane cage to be protected from oxidation and decomposition by the presence of strong bases.
Compared with the traditional coupling method, the method realizes direct B-H activation functionalization, and avoids environmental pollution, dangerous reaction conditions and yield loss in multi-step reaction caused by B (3) preactivation. Compared with the reported B (3) -H activation functionalization method, the reaction uses the toluene reflux condition, and compared with the reported normal-temperature B (3) -H functionalization, the reaction has better solubility and functional group compatibility by taking toluene as a solvent at high temperature. The method can be used for realizing the connection of the C (sp2) or C (sp3) synthetic building block and the carborane B (3) or B (3,6) site. Because the amide substrate in the invention is derived from a corresponding carboxylic acid substrate and is easy to store, the reaction substrate has a wide range and is extremely suitable for late-stage carborane alkylation modification of organic compounds. The reactive amidation of N-acyl-diimides of compounds avoids the formation of B-X (X ═ I, Br, Cl), B-O bonds containing by-products resulting from derivatization of the compounds to halogenated aromatic hydrocarbons, halogenated olefins, halogenated alkanes substrates and possible additives. In addition, the method can be carried out in an enlarged scale, and has a good industrial application prospect.
Detailed Description
The following examples illustrate specific steps of the present invention, but are not intended to limit the invention.
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
Example 1 screening of reaction conditions
According to the conditions shown in Table 1, compound 40(1- [ (1E) -2- (2,4,6-trimethylphenylethenyl) ] -1, 2-dicarbadecaborane, 58.2mg,0.2mmol), active amide (a, b, c, d or E) (0.44mmol), rhodium catalyst (0.01mmol) was added to a dried 10mL Schlenk tube and purged with argon three times. After toluene (1.0mL) was added, the tube was closed. After 24 hours the tube was cooled to room temperature and filtered using 2 cm of celite under a rinse of ethyl acetate. The celite was rinsed with DCM (2X 5 mL). The collected organic solvents were dried and separated by Preparative TLC (PTLC) to give mono-and di-substituents (mono) and (di).
Mes stands for
TABLE 1
The results show that Compound 40 and active amide a are present under standard conditions (5 mol%, [ Rh (cod) Cl)]2Stirred in toluene at 150 ℃ for 24 hours) the product was obtained in 93% isolated yield (mono-: di-11: 82, example 1). Using Rh2(CO)4Cl2The catalyst gave the product in 78% yield under the same conditions (mono-: di-: 20:58, example 2). After switching to the other rhodium catalyst, no desired product was detected (examples 3 to 7). When activated amide b was used, the overall yield dropped to 73% (example 8). When the other three active amides c-e were studied, no product was obtained (examples 9-11). Whereas only traces of product were detected when the temperature was reduced to 100 ℃ (example 10).
Example 2
Preparation of activated amides having N-acyl-diimide groups
the following examples may be used for preparation
Scheme A:
scheme B:
scheme C:
the moiety of the compound having an N-acyl-imide group is selected from the group consisting of:
(2) preparation of mono-/di-carborane alkylated compounds
With reference to the method of example 1, the optimum reaction conditions were selected, and the activated amide obtained in step (1) was cross-coupled with compound 40 to examine the utility of the carborylation (B (3) vertex) reaction under the optimum conditions.
The results show that N-acyl-glutarimides with Electron Donating Groups (EDG) or Electron Withdrawing Groups (EWG) in the para position react smoothly (groups 2-14), while compounds with EWG have better yields (groups 5-18). Methoxy (group 2), 2,4,6-trimethylphenyl (group 3), alkenyl (group 4), pentafluorophenyl (group 5), fluoro (group 6), nitrile (group 7), trifluoromethyl (group 8), oxytrifluoromethyl (group 9), chloride (group 10), bromide (group 11), phosphonyl (group 12), ketone (group 13), C-o-boryl (group 14) are well tolerated (yield up to 95%). After finding the yield reduction due to the para-methoxy group, the present invention installs several EDGs in meta position of N-acyl-glutarimide and finally obtains high yield of the compound (groups 15-17). Large sterically hindered groups, such as cyclohexyl and methyl, hinder the formation of compounds (groups 18 and 19), while less hindered fluorides (group 20) have good yields. The conversion of naphthalene containing substrates (group 21) requires 10 mol% catalyst loading and, in addition, electron rich heteroarylthienyl (group 22), furyl (group 23) or electron deficient pyridyl (group 24) perform well in cross-coupling with B (3) -o-carboranyl under optimized conditions. The yield of less sterically hindered linear alkenyl substrates (groups 25 and 27) is higher. Under the same conditions, the alkyl substrates can also undergo ortho-carborylation (at the B (3) position) in moderate yields (28-30). Molecules containing coordinating atoms such as oxygen and nitrogen can also be readily converted to the corresponding B (3) -o-carboranyl-C (sp2) coupling product (groups 31-39). It has been shown that complex steroid derivatives are excellent couplers, and that the ketone function (group 36), which is extremely sensitive during the coupling process, is not disturbed. The general amide bond is not cleaved under the conditions of the present invention (group 34), demonstrating the ideal selectivity and utility of the process.
All compounds were synthesized as follows unless otherwise specified. Compound 40(58.2mg,0.2mmol), activated amide (0.44mmol for sp2Hybridized amides use N-acyl-glutarimides for sp2The hybridized amide uses N-acyl-succinimide), [ Rh (cod) Cl]2(5.6mg,0.01mmol) was added to a 10mL oven dried Schlenk tube, which was then evacuated three times and placed under Ar. Toluene (1.0mL) was added, the tube was sealed and stirred at 150 ℃. After 24 hours, the tube was cooled to room temperature and filtered using 2 cm of celite under a rinse of ethyl acetate. The celite was rinsed with DCM (2X 5 mL). The collected organic solvent was spun dry and separated by preparative tlc (ptlc) to give the product.
Attention is paid toFor the synthesis of the compounds (groups 21 and 33) [ Rh (cod) Cl ] needs to be used]2(11.2mg,0.02mmol)。
The structure identification results are shown below:
1：
(yield 93%, mono: di 11: 82).
mono：1H NMR(400MHz,CDCl3):δ7.61(d,J＝7.1Hz,2H),7.42–7.29(m,4H),6.71(s,2H),4.70(s,1H),2.19(s,3H),1.51(s,6H)。
11B{H}NMR(125MHz,CDCl3):δ-2.2,-3.1,-8.2,-11.5,-13.9。
13C NMR(100MHz,CDCl3):δ155.0,144.8,134.5,134.4,129.9,128.8,128.4,126.9,73.8,55.8,20.6,17.3。
di：1H NMR(400MHz,CDCl3):δ7.67–7.63(m,4H),7.40–7.29(m,6H),7.23(s,1H),6.56(s,2H),4.85(s,1H),2.11(s,3H),1.01(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ0.2,-1.4,-4.3,-10.5,-12.6。
13C NMR(100MHz,CDCl3):δ153.0,144.6,134.5,134.4,129.8,128.7,127.6,74.7,54.2,20.5,16.7。
2：
(yield 62%, mono: di 30: 32).
mono：1H NMR(400MHz,CDCl3):δ7.52(d,J＝8.6Hz,2H),7.39(s,1H),6.87(d,J＝8.6Hz,2H),6.72(s,2H),4.66(s,1H),3.81(s,3H),2.20(s,3H),1.55(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.3,-3.3,-8.2,-12.0,-13.8。
13C NMR(100MHz,CDCl3):δ161.2,155.1,144.9,135.8,134.5,128.8,126.9,114.0,73.7,55.8,55.2,20.6,17.3。
di：1H NMR(400MHz,CDCl3):δ7.56(d,J＝8.3Hz,4H),7.22(s,1H),6.86(d,J＝8.5Hz,4H),6.59(s,2H),4.77(s,1H),3.81(s,6H),2.14(s,3H),1.10(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ5.8,3.9,0.4,-5.6,-7.4。
13C NMR(100MHz,CDCl3):δ161.2,153.4,144.8,136.0,134.4,128.7,127.6,113.9,74.5,55.2,54.2,20.6,16.7。
3：
(yield 39%, mono: di: 14: 25).
4：
(yield 25%, mono: di 10: 15).
5：
(yield 55%, mono: di 10: 45).
6：
(yield 91%, mono: di 10: 80).
7：
(yield 74%, mono: di: 19: 55).
8：
(yield 95%, mono: di 15: 80).
9：
(yield 83%, mono: di: 12: 71).
10：
(yield 79%, mono: di 25: 54).
11：
(yield 63%, mono: di 25: 38).
12：
(yield 58%).
13：
(yield 68%, mono: di 15: 53).
14：
(yield 58%, mono: di: 34: 24).
mono：1H NMR(400MHz,CDCl3):δ7.82–7.54(m,4H),7.40(s,1H),6.71(s,2H),4.72(s,1H),2.18(s,3H),1.72(s,3H),1.48(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.4,-4.5,-9.2,-9.9,-13.6,-14.8。
13C NMR(100MHz,CDCl3):δ154.6,144.5,134.9,134.8,132.5,130.8,129.0,126.6,81.3,73.8,60.4,55.4,23.3,20.6,17.4。
di：1H NMR(400MHz,CDCl3):δ7.69–7.52(m,8H),7.23(s,1H),6.55(s,2H),4.86(s,1H),2.11(s,3H),1.66(s,6H),0.94(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-0.8,-2.6,-4.6,-10.1。
13C NMR(100MHz,CDCl3):δ152.1,143.6,135.3,135.0,132.6,130.7,129.0,127.2,81.3,74.7,54.0,23.2,20.5,17.2,16.8。
15：
(yield 83%, mono: di: 36: 47).
16：
(yield 75%, mono: di 35: 45).
17：
(yield 73%, mono: di: 21: 52).
18：
(yield 30%).
1H NMR(400MHz,CDCl3):δ7.48(d,J＝7.6Hz,2H),7.36–7.30(m,4H),7.18(s,1H),7.10(ddd,J＝7.7,6.2,2.4Hz,2H),6.50(s,2H),5.04(s,1H),2.08(s,3H),1.90–1.30(m,22H),0.88(s,6H)
11B{1H}NMR(125MHz,CDCl3):δ-2.2,-4.3,-13.3,-13.8。
13C NMR(100MHz,CDCl3):δ154.6,154.0,135.4,134.0,130.2,128.6,128.5,127.5,127.2,125.5,54.5,40.9,34.9,34.7,26.9,26.1,20.5,16.6。
19：
(yield 41%, mono: di 20: 21).
20：
(yield 77%, mono: di 23: 54).
21：
(yield 76%, mono: di 20: 56).
22：
(yield 90%, mono: di: 18: 72).
mono：1H NMR(400MHz,CDCl3):δ7.49(dd,J＝4.8,1.0Hz,1H),7.46(s,1H),7.34(dd,J＝3.4,1.0Hz,1H),7.09(dd,J＝4.9,3.4Hz,1H),6.47(s,2H),4.69(s,1H),2.21(s,3H),1.62(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-1.3,-4.4,-10.2,-12.3。
13C NMR(100MHz,CDCl3):δ154.8,144.7,135.7,134.7,131.1,128.9,128.6,127.0,73.8,57.2,20.6,17.2。
di：1H NMR(400MHz,CDCl3):δ7.49(dd,J＝4.8,1.0Hz,2H),7.37(dd,J＝3.4,1.0Hz,2H),7.35(s,1H),7.08(dd,J＝4.8,3.4Hz,2H),6.66(s,2H),4.86(s,1H),2.17(s,3H),1.28(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-1.7,-4.5,-10.3,-12.4。
13C NMR(100MHz,CDCl3):δ152.0,144.2,136.0,134.8,131.2,128.9,128.4,128.0,74.4,56.4,20.6,16.7。
23：
(yield 82%, mono: di 22: 60).
mono：1H NMR(400MHz,CDCl3):δ7.51(d,J＝1.7Hz,1H),7.48(s,1H),6.82(d,J＝3.3Hz,1H),6.77(s,2H),6.38(dd,J＝3.3,1.7Hz,1H),4.73(s,1H),2.22(s,3H),1.73(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.2,-3.1,-4.7,-6.4,-8.1,-10.6,-11.9,-13.0。
13C NMR(100MHz,CDCl3):δ154.8,146.4,134.6,129.1,128.9,126.9,120.8,110.8,73.6,56.8,20.7,17.5。
di：1H NMR(400MHz,CDCl3):δ7.50(s,2H),7.37(d,J＝1.5Hz,1H),6.86(d,J＝3.2Hz,2H),6.70(s,2H),6.38(dd,J＝3.2,1.7Hz,2H),4.89(s,1H),2.19(s,3H),1.50(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ3.8,0.3,-4.6,-6.5,-7.6。
13C NMR(100MHz,CDCl3):δ152.9,146.2,134.5,128.8,128.0,127.4,121.0,110.9,74.4,56.2,20.6,17.1。
24：
(yield 83%, mono: di: 36: 47).
mono：1H NMR(400MHz,CDCl3):δ8.36(dd,J＝2.2Hz,0.8Hz,1H),7.73(dd,J＝8.4Hz,2.2Hz,1H),7.40(s,1H),6.72(s,2H),6.70(d,J＝0.8Hz,1H),4.67(s,1H),3.92(s,3H),2.19(s,3H),1.57(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-1.9,-3.0,-7.9,-11.3,-13.6。
13C NMR(100MHz,CDCl3):δ186.6,166.9,154.8,152.6,143.9,134.7,128.9,126.7,110.9,74.2,55.3,53.5,20.6,17.4。
di：1H NMR(400MHz,CDCl3):δ8.38(dd,J＝2.2,0.8,2H),7.73(dd,J＝8.4Hz,2.2Hz,2H),7.25(s,1H),6.68(dd,J＝8.5Hz,0.7Hz,2H),6.60(s,2H),4.77(s,1H),3.91(s,6H),2.12(s,3H),1.13(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-0.3,-3.8,-10.2,-12.4。
13C NMR(100MHz,CDCl3):δ165.3,152.8,144.2,144.0,134.9,129.2,129.0,127.4,110.8,74.2,53.9,53.6,20.5,16.9。
25：
(yield 96%, mono: di: 16: 80).
mono：1H NMR(400MHz,CDCl3):δ7.46(s,1H),7.32(d,J＝7.4Hz,2H),7.28–7.17(m,
3H)7.09(d,J＝18.1Hz,1H),6.71(s,2H),6.20(d,J＝18.1Hz,1H),4.41(s,1H),2.14(s,3H),1.86(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ2.9,2.4,-3.4,-4.0,-6.6,-8.4,-9.6。
13C NMR(100MHz,CDCl3):δ155.5,147.4,145.0,137.1,134.7,129.0,128.8,128.6,126.8,126.6,118.3,72.8,56.3,20.6,18.2。
di：1H NMR(400MHz,CDCl3):δ7.41(s,1H),7.30(d,J＝8.0Hz,4H),7.27–7.15(m,6H),7.11(d,J＝18.1Hz,2H),6.66(s,2H),6.23(d,J＝18.2Hz,2H),4.33(s,1H),2.10(s,3H),1.83(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ3.0,0.8,-6.2。
13C NMR(100MHz,CDCl3):δ154.4,147.2,145.0,137.2,134.8,129.2,128.64,128.57,127.4,126.6,119.1,73.0,56.5,20.6,18.3。
26：
(yield 47%).
27：
(yield 84%, mono: di-18: 66).
28：
(yield 62%, mono: di 23: 39).
mono：1H NMR(400MHz,CDCl3):δ7.60(s,1H),7.31–7.26(m,2H),7.22–7.18(m,3H),6.86(s,2H),4.34(s,1H),2.95–2.89(m,2H),2.28(s,3H),2.05(s,6H),1.47–1.41(m,2H)。
11B{1H}NMR(125MHz,CDCl3):δ-1.0,-2.8,-9.0,-12.2。
13C NMR(100MHz,CDCl3):δ155.5,144.8,143.3,135.0,129.3,128.4,127.8,127.0,125.9,73.0,57.0,33.9,20.7,18.5,16.0(br)。
di：1H NMR(400MHz,CDCl3):δ7.57(s,1H),7.29–7.23(m,4H),7.20–7.14(m,6H),6.88(s,2H),4.07(s,1H),2.96–2.83(m,4H),2.28(s,3H),2.12(s,6H),1.42–1.38(m,4H)。
11B{1H}NMR(125MHz,CDCl3):δ0.03,-2.7,-3.5,-12.0。
13C NMR(100MHz,CDCl3):δ154.0,144.1,143.5,135.6,129.7,129.3,128.4,128.1,127.8,125.8,73.5,58.1,34.0,20.7,18.9,16.8(br)。
29：
(yield 56%).
1H NMR(400MHz,CDCl3):δ7.82(dd,J＝5.4Hz,3.0Hz,2H),7.70(dd,J＝5.5Hz,3.0Hz,2H),7.59(s,1H),6.80(s,2H),4.40(s,1H),3.95(dd,J＝9.5Hz,7.3Hz,2H),2.23(s,3H),2.01(s,6H),1.55–1.51(m,2H)。
11B{1H}NMR(125MHz,CDCl3):δ2.7,-3.7,-6.7。
13C NMR(100MHz,CDCl3):δ168.1,155.0,135.0,133.9,132.0,129.2,127.0,123.2,73.1,57.2,36.7,20.6,18.4,14.4(br)。
HRMS m/z(ESI):calcd for C22H30B10N2O2(M+H)+,465.3316,found。
30：
(yield 51%).
1H NMR(400MHz,CDCl3):δ7.55(s,1H),6.86(s,2H),5.77(m,1H),5.04–4.89(m,2H),4.25(s,1H),2.26(s,3H),2.11(m,2H),2.05(s,6H),1.67–1.63(m,2H),1.08–0.99(m,2H)。
11B{1H}NMR(125MHz,CDCl3):δ-0.7,-2.9,-9.1,-12.5。
13C NMR(100MHz,CDCl3):δ155.7,138.3,134.9,129.2,126.9,115.1,72.9,57.0,36.3,27.5,20.7,18.5,14.0(br)。
31：
(yield 54%, mono: di: 21: 33).
32：
(yield 56%, mono: di: 32: 24).
33：
(yield 39%).
1H NMR(400MHz,CDCl3):δ8.39(s,1H),8.21(d,J＝7.7Hz,1H),7.78(t,J＝7.8Hz,1H),7.67(s,1H),7.45(s,1H),7.43(d,J＝8.1Hz,1H),6.65(s,2H),4.85(s,1H),2.45(s,3H),2.43(s,3H),2.13(s,3H),1.53(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ2.9,-2.7,-4.3,-5.7,-6.8,8.0。
13C NMR(100MHz,CDCl3):δ181.7,180.6,169.4,169.0,154.2,153.1,151.0,150.0,149.7,144.4,135.6,134.8,134.2,133.6,130.6,130.5,128.9,126.6,126.1,125.6,74.1,55.6,21.0,20.6,18.1,17.5。
34：
(yield 78%, mono: di 32: 46).
mono：1H NMR(500MHz,CDCl3):δ8.04(dd,J＝4.9Hz,2.0Hz,1H),7.84(dt,J＝7.6Hz,1.6Hz,1H),7.54–7.46(m,4H),7.37(s,1H),7.30(d,J＝7.7Hz,2H),7.17–7.07(m,2H),7.00(dd,J＝7.5Hz,4.9Hz,1H),6.95(s,1H),6.72–6.64(m,3H),6.60(s,1H),5.40(d,J＝15.1Hz,1H),4.71(d,J＝15.7Hz,1H),4.67(s,1H),2.19(s,3H),1.48(s,6H)。
11B{1H}NMR(156MHz,CDCl3):δ2.49,-2.86,-6.47,-7.83。
13C NMR(125MHz,CDCl3):δ167.2,162.0(dd,J＝252.3Hz,11.4Hz),157.7(dd,J＝253.1Hz,12.4Hz),157.3,154.7,153.0,148.5,144.6,138.9,138.2,134.7,134.6,131.8(q,J＝32.8Hz),131.0(d,J＝9.7Hz),130.0,129.1,128.8,126.8,125.5(dd,J＝12.2Hz,4.0Hz),124.65,124.59,121.7(q,J＝3.5Hz),120.8,118.8,118.3(q,J＝3.7Hz),111.5(dd,J＝22.3Hz,3.4Hz),104.9(t,J＝25.4Hz),73.7,55.6,52.2,20.6,17.2,
19F NMR(376MHz,CDCl3):δ-62.2(s,3F),-107.4(s,1F),-113.7(s,1F)。
di：1H NMR(500MHz,CDCl3):δ8.13(dd,J＝4.9Hz,1.7Hz,2H),7.91(d,J＝7.4,2H),7.65–7.56(m,8H),7.40–7.30(m,5H),7.21(s,4H),7.09(dd,J＝7.4Hz,5.0Hz,2H),6.99–6.92(m,2H),6.72(s,2H),6.61–6.58(m,4H),5.49(d,J＝15.4Hz,2H),4.85(s,1H),4.76(d,J＝14.9Hz,2H),2.20(s,3H),1.06(s,6H)。
11B{1H}NMR(156MHz,CDCl3):δ-1.7,-4.0,-12.7。
13C NMR(125MHz,CDCl3):δ167.2,161.9(dd,J＝252.2Hz,11.3Hz),157.7(dd,J＝253.1Hz,12.3Hz),157.3,153.1,152.8,148.6,144.2,138.9,138.0,134.7,134.6,131.8(q,J＝32.7Hz),131.0(q,J＝6.7Hz),130.1,128.7,128.0(d,J＝10.9Hz),127.5,125.4(dd,J＝12.2Hz,3.8Hz),124.6,123.6(q,J＝272.4Hz),121.6(q,J＝3.5Hz),120.9,118.8,118.3(q,J＝3.6Hz),111.5(d,J＝22.1Hz),104.9(t,J＝25.0Hz),74.5,54.4,52.1,20.4,16.8。
19F NMR(376MHz,CDCl3):δ-62.1(s,6F),-107.5(s,2F),-113.7(s,2F)。
35：
(yield 63%, mono: di 45: 18).
mono：1H NMR(400MHz,CDCl3):δ7.53(d,J＝8.5Hz,2H),7.37(s,1H),6.94(d,J＝8.0Hz,2H),6.70(s,2H),5.37–5.23(m,2H),5.17(td,J＝9.4Hz,2.8Hz,1H),5.06(dd,J＝7.5Hz,2.2Hz,1H),4.65(s,1H),4.29(ddd,J＝12.3Hz,5.4Hz,3.6Hz,1H),4.15(ddd,J＝12.4Hz,5.5Hz,2.5Hz,1H),3.85(ddd,J＝10.1Hz,5.3Hz,2.5Hz,1H),2.18(s,3H),2.09–1.96(m,12H),1.53(s,3H),1.52(s,3H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.6,-8.3,-13.1。
13C NMR(100MHz,CDCl3):δ170.5,170.3,169.4,169.3,158.4,154.9,144.7,135.9,134.7,128.9,126.8,116.7,98.7,74.4,73.8,72.6,72.1,71.1,68.2,61.9,57.2,55.6,20.6,17.8,17.32,17.29。
di：1H NMR(400MHz,CDCl3):δ7.54(d,J＝8.6Hz,4H),7.18(s,1H),6.91(d,J＝7.3Hz,4H),6.55(s,2H),5.35–5.21(m,4H),5.15(td,J＝9.6Hz,1.3Hz,2H),5.05(dd,J＝7.4Hz,3.0Hz,2H),4.75(s,1H),4.27(dd,J＝12.3Hz,5.2Hz,2H),4.12(ddd,J＝12.0Hz,3.7Hz,2.3Hz,2H),3.83(ddd,J＝10.0Hz,5.2Hz,2.4Hz,2H),2.11(s,3H),2.06–2.00(m,24H),1.02(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-0.6,-4.0,-11.7。
13C NMR(100MHz,CDCl3):δ170.44,170.42,170.2,169.3,169.2,158.3,152.9,144.3,140.0,134.7,128.8,127.4,116.6,98.7,98.6,74.4,72.5,72.0,71.0,68.2,61.8,54.1,20.54,20.53,20.4,16.6。
36：
(yield 72%, mono: di: 42: 30).
mono：1H NMR(400MHz,CDCl3):δ7.61(d,J＝8.2Hz,2H),7.42–7.34(m,3H),7.20(d,J＝8.6Hz,1H),6.77(d,J＝2.9Hz,1H),6.72(d,J＝2.8Hz,1H),6.69(s,2H),5.04(s,2H),4.69(s,1H),2.90(dd,J＝8.0Hz,5.0Hz,2H),2.51(dd,J＝18.8Hz,8.6Hz,1H),2.44–2.37(m,1H),2.27(td,J＝10.5Hz,3.9Hz,1H),2.22–1.92(m,7H,4H from Estrone and 3H from Mes),1.37–1.07(m,12H,6H from Estrone and 6H from Mes),0.91(s,3H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.6,-8.2,-9.2,-11.7,-13.7。
13C NMR(100MHz,CDCl3):δ221.0,156.6,155.0,144.8,139.4,137.9,134.6,134.3,132.4,128.8,127.1,126.9,126.4,114.9,112.3,73.8,69.3,55.7,50.4,48.0,44.0,38.4,35.9,31.6,29.7,26.6,26.0,21.6,20.7,17.4,13.9。
di：1H NMR(400MHz,CDCl3):δ7.63(d,J＝8.0Hz,4H),7.36(d,J＝7.8Hz,4H),7.20(m,3H),6.80–6.66(m,4H),6.51(s,2H),5.02(s,1H),2.88(dd,J＝7.1Hz,3.5Hz,4H),2.51(dd,J＝18.8Hz,8.5Hz,2H),2.43–2.36(m,2H),2.30–2.22(m,2H),2.21–1.93(m,12H),1.70–1.36(m,12H),1.26(s,3H),0.95(s,6H),0.90(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ；-0.6,-10.4。
13C NMR(100MHz,CDCl3):δ220.9,156.6,153.0,144.6,139.2,137.8,134.7,134.3,132.4,128.7,127.5,126.9,126.3,114.9,112.3,74.6,69.3,54.1,50.4,48.0,44.0,38.3,35.8,31.6,29.6,26.5,25.9,21.6,20.5,16.7,13.8。
37：
(yield 37-91%).
1H NMR(400MHz,CDCl3):δ7.64(d,J＝7.3Hz,4H),7.59(d,J＝7.9Hz,2H),7.33–7.28(m,3H),7.26–7.11(m,4H),6.77(d,J＝8.8Hz,2H),6.57(s,2H),6.27(d,J＝18.2Hz,1H),5.01(hept,J＝6.2Hz,1H),4.62(s,1H),2.07(s,3H),1.59(s,6H),1.41(s,6H),1.14(s,3H),1.12(s,3H)。
11B{1H}NMR(125MHz,CDCl3):δ-2.0,-11.7。
13C NMR(100MHz,CDCl3):δ194.9,173.1,159.7,153.5,147.4,144.6,139.2,137.2,134.9,134.4,132.0,130.2,129.2,129.1,128.8,128.6,127.4,126.7,117.2,79.4,73.9,69.4,55.5,30.9,25.42,25.37,21.6,20.6,17.7.
HRMS m/z(ESI):calcd for C40H49B10NO4(M+H)+718.4670,found 718.4674。
38：
(yield 38-63%).
1H NMR(500MHz,CDCl3):δ7.57(d,J＝8.1Hz,2H),7.36(d,J＝7.1Hz,3H),7.17(s,1H),7.06(s,1H),6.85(s,1H),6.69(s,2H),5.15(s,1H),3.81(s,3H),3.71(s,3H),3.67(s,2H),2.50(s,3H),2.17(s,3H),1.50(s,6H)。
11B{1H}NMR(156MHz,CDCl3):δ-3.3,-8.2,-12.2。
13C NMR(125MHz,CDCl3):δ171.1,188.1,159.0,155.7,145.2,139.4,137.5,134.3,133.8,132.3,130.92,130.86,129.2,128.7,126.6,123.9,112.2,99.4,73.7,57.0,55.6,52.2,30.1,20.6,17.2,13.2。
HRMS m/z(ESI):calcd for C32H40B10ClN2O4(M+H)+661.3607,found 661.3600。
39：
(yield 39-87%).
1H NMR(400MHz,CDCl3):δ7.69(d,J＝7.8Hz,2H),7.56(dd,J＝10.3,7.4Hz,4H),7.33–7.17(m,4H),6.85(d,J＝2.5Hz,1H),6.74(d,J＝9.0Hz,1H),6.51(s,2H),6.35(dd,J＝9.0,2.6Hz,1H),4.79(s,1H),3.73(s,3H),3.62(s,3H),3.57(s,2H),2.24(s,3H),2.04(s,3H),1.06(s,6H)。
11B{1H}NMR(125MHz,CDCl3):δ-0.9,-11.8。
13C NMR(100MHz,CDCl3):δ171.4,168.8,156.0,152.6,144.1,136.5,136.0,134.9,134.8,134.5,130.8,130.6,130.0,129.2,129.0,128.3,127.6,115.0,112.3,111.3,101.4,78.6,74.7,55.7,54.6,52.2,30.2,20.5,17.1,13.4.
HRMS m/z(ESI):calcd for C38H45B10N2O4(M+H)+703.4310,found 703.4316。
Example 5 further conversion of B (3)/B (3,6) -o-carborane alkylate
(1) In the case of compound 1, gram-weight synthesis was performed
Compound 40(1000.0mg,3.44mmol), active amide a (1650.0mg,7.57mmol), [ Rh (cod) Cl, were added to a 200mL sealable Schlenk tube as previously described]2(96.3mg,0.17 mmol). The atmosphere was changed to Ar by pumping three times, and 17mL of toluene was added. Column chromatography gave 1-mono (185.6mg,0.52mmol, 15%) and 1-di (1141.9mg,2.61mmol, 76%).
Claims (1)
1. A process for the B (3)/B (3,6) -o-carborane alkylation of compounds characterized in that a compound of an activated amide having an N-acyl-imide group is reacted in the presence of an Rh catalyst [ Rh (cod) Cl ]]2And/or Rh2(CO)4Cl2Catalytically, and cross-coupling with o-carborane with an imine group on a cage carbon, wherein the reaction formula is as follows:
alternatively, the first and second electrodes may be,
R1represents H, C1-C10 alkyl, and n is an integer of 1-5; r2、R3Represents:
ar represents phenyl, thienyl, furyl, pyridyl and pyrimidyl which are substituted by one or more of H, methyl, ethyl, propyl, isopropyl, butyl and tert-butyl;
the reaction temperature is 130-150 ℃, and the reaction solvent is one or more selected from toluene, o-xylene, m-xylene or p-xylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010844238.8A CN112028919B (en) | 2020-08-20 | 2020-08-20 | B (3)/B (3,6) -o-carborane alkylation method of compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010844238.8A CN112028919B (en) | 2020-08-20 | 2020-08-20 | B (3)/B (3,6) -o-carborane alkylation method of compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112028919A CN112028919A (en) | 2020-12-04 |
| CN112028919B true CN112028919B (en) | 2021-05-14 |
Family
ID=73581012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010844238.8A Active CN112028919B (en) | 2020-08-20 | 2020-08-20 | B (3)/B (3,6) -o-carborane alkylation method of compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112028919B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591357B (en) * | 2022-03-07 | 2023-05-16 | 郑州大学 | Synthesis method of B (9) -amino o-carborane compound |
| CN114736228B (en) * | 2022-04-11 | 2024-01-30 | 陕西师范大学 | Fluorescence sensing film based on pyromellitic acid diimide derivative modified by o-carborane, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303194A (en) * | 2020-04-07 | 2020-06-19 | 西安近代化学研究所 | Synthesis method of B (4,5) alkenyl substituted carborane derivative |
-
2020
- 2020-08-20 CN CN202010844238.8A patent/CN112028919B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303194A (en) * | 2020-04-07 | 2020-06-19 | 西安近代化学研究所 | Synthesis method of B (4,5) alkenyl substituted carborane derivative |
Non-Patent Citations (3)
| Title |
|---|
| Pyridyl-Directed Cp*Rh(III)-Catalyzed B(3)−H Acyloxylation of o‑Carborane;Chun-Xiao Li等;《Organic Letters》;20170920;第19卷;第5178-5181页 * |
| Rhodium catalyzed cascade cyclization featuring B–H and C–H activation:one-step construction of carborane-fused N-poly heterocycles;Hairong Lyu等;《Chem.Sci.》;20180629;第9卷;第6390-6394页 * |
| Transition-Metal-Catalyzed Regioselective Functionalization of Monophosphino-o-Carboranes;Zi-Yang Zhang等;《Chemistry—A European Journal》;20200326;第26卷;第5307-5050页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112028919A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Radical decarboxylative carbometalation of benzoic acids: a solution to aromatic decarboxylative fluorination | |
| El-Zaria et al. | m-Carborane-based chiral NBN pincer-metal complexes: synthesis, structure, and application in asymmetric catalysis | |
| Moghaddam et al. | Palladium-catalyzed carbamate-directed regioselective halogenation: a route to halogenated anilines | |
| Soro et al. | Synthesis of the first C-2 cyclopalladated derivatives of 1, 3-Bis (2-pyridyl) benzene. Crystal structures of [Hg (NCN) Cl],[Pd (NCN) Cl], and [Pd2 (NCN) 2 (μ-OAc)] 2 [Hg2Cl6]. Catalytic activity in the Heck reaction | |
| CN112028919B (en) | B (3)/B (3,6) -o-carborane alkylation method of compound | |
| Chen et al. | A new, efficient, and inexpensive copper (II)/salicylic acid complex catalyzed Sonogashira-type cross-coupling of haloarenes and iodoheteroarenes with terminal alkynes | |
| JP6218153B2 (en) | Ligand, metal complex containing the ligand, and reaction using the metal complex | |
| Nelson et al. | Chemo-, regio-, and stereoselective copper (II)-catalyzed boron addition to acetylenic esters and amides in aqueous media | |
| Gunay et al. | Cleavage of Carbon− Carbon Bonds of Diphenylacetylene and Its Derivatives via Photolysis of Pt Complexes: Tuning the C− C Bond Formation Energy toward Selective C− C Bond Activation | |
| EP3856734A1 (en) | Reagents and process for direct c-h functionalization | |
| Kilic et al. | Synthesis, spectroscopic and catalytic properties of some new boron hybrid molecule derivatives by BF2 and BPh2 chelation | |
| Xu et al. | Synthesis and Structural Characterization of Palladacycles with Polydentate Ligands by a Stepwise Coupling Route–Palladacycles Containing Halides as Efficient Catalysts and Substrates | |
| Bjelopetrovic et al. | A detailed kinetico-mechanistic investigation on the palladium C–H bond activation in azobenzenes and their monopalladated derivatives | |
| Song et al. | Nickel-Catalyzed Remote C (sp3)–N/O Bond Formation of Alkenes with Unactivated Amines and Alcohols | |
| Belkova et al. | Influence of phosphine (pincer) ligands on the transition metal hydrides reactivity | |
| Wong et al. | Air-Stable Iron-Based Precatalysts for Suzuki–Miyaura Cross-Coupling Reactions between Alkyl Halides and Aryl Boronic Esters | |
| Zu et al. | Copper (II)-catalyzed direct amination of 1-naphthylamines at the C8 site | |
| Jiang et al. | Merging Visible Light Photocatalysis and P (III)‐Directed C− H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands | |
| Masuda et al. | Late-Stage Functionalization of the Periphery of Oligophenylene Dendrimers with Various Arene Units via Fourfold C–H Borylation | |
| CN114478609B (en) | Method for using thiophenol photocatalyst in defluorination alkylation or defluorination protonation reaction | |
| Jia et al. | Three copper (II) complexes derived from 2‐methylquinoline and cyclic secondary amines: Synthesis and catalytic application in C—N bond forming reactions | |
| Reyes-Mata et al. | Calix [8] arene-based Ni (II) complexes for electrocatalytic CO2 reduction | |
| Bergens et al. | Synthesis and structure of a biphenanthrol-palladium complex displaying an unusual bonding mode | |
| Iglesias et al. | Fluoro aromatic imine nickel (0) complexes: Synthesis and structural studies | |
| Yang et al. | Macrocyclic Aryl–Nickel (II) complexes: Synthesis, structure, and reactivity studies |
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 |