CN114853797B - Preparation method of alpha-amino boron ring compound - Google Patents

Preparation method of alpha-amino boron ring compound Download PDF

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CN114853797B
CN114853797B CN202210620520.7A CN202210620520A CN114853797B CN 114853797 B CN114853797 B CN 114853797B CN 202210620520 A CN202210620520 A CN 202210620520A CN 114853797 B CN114853797 B CN 114853797B
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CN114853797A (en
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王洪根
刘源
刘培庆
陈志豪
张湘东
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Sun Yat Sen University
Guangzhou Zhongda Nansha Technology Innovation Industrial Park Co Ltd
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Sun Yat Sen University
Guangzhou Zhongda Nansha Technology Innovation Industrial Park 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • 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
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of an alpha-amino boron ring compound. The method comprises the steps of preparing the selenium-enriched iodine-enriched catalyst by using a selenium catalyst and a high-valence iodine oxidantUnder the existence condition, enabling an allyl boron compound to react with sulfonamide or sulfonic acid amine to obtain an alpha-amino boron compound; the structural formula of the allylboron compound is shown as a formula (1), the structural formula of the sulfonamide is shown as a formula (2), and the structural formula of the sulfonic acid amine is shown as a formula (3); the structural formula of the alpha-amino boron-based compound is shown as a formula (4) or (5);

Description

Preparation method of alpha-amino boron ring compound
Technical Field
The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of an alpha-amino boron ring compound.
Background
The discovery of alpha-aminoboronic acid compounds with application value in biological medicine, such as bortezomib (bortezomib), represents an important research progress in the field, and is an important treatment method for solving multiple myeloma and mantle cell lymphoma at present. The alpha-aminoboronic acid structure in bortezomib L-boroleucine is critical for its protease inhibitory activity. In addition, the alpha-aminoboric acid is applied to various aspects such as fluorescent tracers, carbohydrate sensors and the like.
The development of a novel synthesis method of the alpha-aminoboric acid compound has important significance in the fields of biological medicine, sensors and the like. There are many reports on the current methods for synthesizing alpha-aminoboronic acid compounds, including two aspects of constructing C-N from organoborides and C-B bonds from amino compounds:
the method for synthesizing alpha-aminoboron compounds by constructing C-B bonds can be mainly divided into the following categories, namely, using alpha-amino groupsReaction of a metal reagent with a boron-containing electrophile, reaction of a nucleophilic boron compound with an imine compound, hydroboration of an amide compound, and C (sp 3 ) Direct boration of the H bonds. The synthetic route for the reaction of the alpha-amino metal reagent with the boron-containing electrophile is shown below:
the synthetic route for the reaction of nucleophilic boron compounds with imine compounds is shown below:
the synthetic route for the borohydride reaction of the amide compound is shown below:
C(sp 3 ) The synthetic route for the direct boration reaction of the H bond is as follows:
the method for synthesizing the alpha-amino boron compound by constructing the C-B bond mainly comprises the following steps of reacting alpha-halogenated boric acid ester with an amino nucleophile, wherein the synthetic route is as follows:
although the synthesis of α -aminoboron compounds has been attracting attention and many strategies have been available to achieve the synthesis of a variety of α -aminoboron compounds, these methods have disadvantages such as more or less severe reaction conditions, poor substrate universality, low yields, the need to modify the reaction substrate by multiple units, and the inability to synthesize α -aminoboron compounds with more complex structures and more abundant functional groups, and the difficulty in constructing chiral centers at the α -position to achieve highly enantioselective synthesis of α -aminoboron compounds. How to develop and construct a novel efficient synthesis method of the alpha-amino boron compound is beneficial to activity research and application of the alpha-amino boron compound.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an alpha-amino boron ring compound, which can construct various types of alpha-amino boron ring compounds, has wide substrate application range, and can be directly used for reaction without any pretreatment and modification of reactants; meanwhile, the reaction condition is mild, high temperature or high pressure is not needed, an acid or alkali additive is not needed, and the operation is simple and convenient, so that the method is a method for efficiently synthesizing the alpha-amino boron-type ring compound.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of an alpha-amino boron-based compound comprises the following steps: under the existence of selenium catalyst and high-valence iodine oxidant, making allylboron compound and sulfonamide or amine sulfonate react to obtain alpha-aminoboron compound;
the structural formula of the allylboron compound is shown as a formula (1), the structural formula of the sulfonamide is shown as a formula (2), and the structural formula of the sulfonic acid amine is shown as a formula (3); the structural formula of the alpha-amino boron-based compound is shown as a formula (4) or (5);
wherein R is 1 Is C 1 ～C 10 C is a hydrocarbon group of (C) 1 ～C 10 Substituted hydrocarbyl, halogen, phenyl, substituted phenyl, heterocycle Aryl, heterocyclic aryl containing substituent, cyano, ketocarbonyl, ester, ether, benzyloxy, substituted benzyloxy, siloxane or dioxan;
R 2 h, C of a shape of H, C 1 ～C 6 Or a hydrocarbyl, phenyl or substituted phenyl group, or R 2 And R is R 1 Connected into a ring;
R 3 is H or C 1 ～C 6 Is a hydrocarbon group of (2);
R 4 is C 1 ～C 10 Is a hydrocarbon group of (2);
R 5 、R 6 each independently is C 1 ～C 6 C is a hydrocarbon group of (C) 1 ～C 6 Substituted hydrocarbyl, phenyl or substituted phenyl of (a).
According to the invention, an allylboron compound and sulfonamide or amine sulfonate are taken as starting compounds, at least one hydrogen is arranged at the alpha position of olefin of the allylboron compound, and two hydrogens are arranged on nitrogen of the sulfonamide or amine sulfonate, so that an ammonification reaction mainly occurs at the alpha position of boron due to the influence of boron on a substrate.
The reaction process is as follows:
wherein R' NH 2 Is sulfonamide shown as a formula (2) or amine sulfonate shown as a formula (3).
Specifically, an allylboron compound is taken as an initial compound A, a selenium catalyst and a sulfonamide or sulfonic acid amine compound firstly generate a selenimine compound under the action of an oxidant, the selenimine compound and the initial compound realize the generation of carbon selenium bonds and the migration of double bonds to generate an intermediate B (the reaction is more prone to the reaction of A to B and the reaction of A to B' is less prone to occur under the condition of the invention) through an ene reaction (alkene reaction) process, and the compound B generates a final allylalpha-amino boron compound through a [2,3] -sigmatropic migration (single bond transfer) process.
The invention adopts specific allyl boron compounds and specific sulfonamide or sulfonic acid amine compounds as starting materials, and can prepare the allyl alpha-amino boron compounds without high temperature and high pressure in the presence of a selenium catalyst and a high-valence iodine oxidant. The method has mild reaction conditions and simple operation, and meanwhile, the method has wide substrate applicability and can prepare various allyl alpha-amino boron compounds. By adopting specific starting materials, the starting materials can be directly used for reaction without any other treatment or modification, the reaction steps are few, and the process is simple.
Preferably, the C 1 ～C 10 Is selected from C 1 ～C 10 Fatty alkyl, C 1 ～C 10 Cycloalkane, C 1 ～C 10 Aliphatic alkylene group, C 1 ～C 10 One of the fatty alkyne groups; the C is 1 ～C 10 Substituted hydrocarbyl of (2) is selected from halogen, cyano, phenyl, hydroxy, amino, sulfonic acid, p-benzenesulfonic acid, azide, benzyloxy, substituted benzyloxy, siloxane, and siloxy substituted C 1 ～C 10 Fatty alkyl, C 1 ～C 10 Naphthene radical, C 1 ～C 10 Aliphatic alkylene or C 1 ～C 10 Aliphatic alkyne groups.
Preferably, the C 1 ～C 10 Is selected from C 1 ～C 6 Is a hydrocarbon group of (a). The C is 1 ～C 10 Is selected from C 1 ～C 6 Substituted hydrocarbyl of (c).
Preferably, the halogen is selected from one of Cl, br, F or I, more preferably Cl or F.
Preferably, the substituted phenyl is selected from C 1 ～C 6 Alkanes, halogens, nitro, cyano, hydroxy, sulfonic acid groups, C 1 ～C 6 Phenyl substituted by one or more groups in alkoxy.
Preferably, the heterocyclic aromatic hydrocarbon group is selected from C 5 ～C 20 More preferably, the heterocyclic aromatic hydrocarbon group containing any one of the elements N, S, O is selected from furyl, pyrrolyl, thienyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinolinyl, and isozylQuinolinyl, benzofuranyl, indolyl, triazolyl, benzotriazolyl or phthalimidyl.
Preferably, the substituent in the heterocyclic aromatic hydrocarbon group containing a substituent is selected from C 1 ～C 6 One or more of alkane, halogen, cyano, phenyl, hydroxy, sulfonic acid, p-benzenesulfonic acid, azide, carbonyl.
Preferably, the ester group is selected from the group consisting of-R 1a -COO-R 1b Or R is 1a -COO-R 1b -, wherein R is 1a 、R 1b Are independently selected from C 1 ～C 14 A hydrocarbyl group, a phenyl group, or a substituted phenyl group.
Preferably, the ether group is selected from the group consisting of-R 1c -O-R 1d Wherein R is 1a 、R 1b Are independently selected from C 1 ～C 14 A hydrocarbyl group, a phenyl group, or a substituted phenyl group.
Preferably, the substituted benzyloxy group is selected from the group consisting of C contained in a benzene ring 1 ～C 6 Benzyloxy of one or more substituents selected from alkane, halogen, cyano, phenyl, hydroxy, sulfonic acid, p-benzenesulfonic acid, azide and carbonyl.
Preferably, the siloxane groups are selected from the group consisting of-OSiR 1e R 1f R 1g Wherein R is 1e 、R 1f 、R 1g Are independently selected from C 1 ～C 14 Hydrocarbon radicals (more preferably C 1 ～C 10 More preferably C 1 ～C 6 A hydrocarbyl group), a phenyl group, or a substituted phenyl group.
Preferably, the C 1 ～C 6 Is selected from C 1 ～C 6 Fatty alkane, C 1 ～C 6 Cycloalkane, C 1 ～C 6 Fatty olefins, C 1 ～C 6 One of the aliphatic alkynes.
Preferably, R 1 Methyl, propyl, butyl, chloro-substituted butyl, decyl, cyclopentyl, cyclohexyl, butenyl, phenethyl, benzyl, 4-butylbutyl, One of them.
Preferably, R 2 H, C of a shape of H, C 1 ～C 4 More preferably R 2 Is one of H, cyclopropyl, methyl, butyl, ethyl, phenyl, benzyl and cyclopentyl.
Preferably, R 2 And R is R 1 When the two are connected into a ring, the two are connected into an n-membered ring, and n is more than or equal to 4. Preferably linked as a four-, five-, six-, seven-or eight-membered ring. The n-membered ring has 1 or more double bonds, preferably 1 double bond. The n-membered ring is an unsubstituted or substituted n-membered ring; when the n-membered ring has a substituent, the substituent may be selected from C 1 ～C 10 C is a hydrocarbon group of (C) 1 ～C 10 Substituted hydrocarbyl, halogen, phenyl, substituted phenyl, heterocyclic aromatic, substituted heterocyclic aromatic, cyano, ketocarbonyl, ester, ether, benzyloxy, substituted benzyloxy, silane, dioxanyl.
Preferably, R 3 Is H or methyl.
Preferably, R 4 Is methyl, six-membered cycloalkyl or
Preferably, R 5 Is methyl, phenyl, trifluoromethyl, p-bromophenyl, p-fluorophenyl, p-tolyl, p-chlorophenyl, 4-t-butylphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl or o-nitrophenyl.
Preferably, R 6 Is trifluoromethyl, trifluoroethyl, trichloroethyl, phenyl, p-methoxyphenyl, 4-methyl phenyl, hexafluoroisopropyl or trifluoroethyl.
Preferably, the selenium catalystIncluding IMeSe, IBuSe, cy 3 Se、Ph 3 At least one of the PSes, more preferably IMeSE.
Preferably, the hypervalent iodine oxidizer comprises at least one of alkyl carboxylic acid iodobenzene, more preferably iodobenzene diacetate, iodobenzene phenylacetate, iodobenzene phenylpropionate, iodobenzene pivalate, iodobenzene trifluoroacetate, iodobenzene acetate, and still more preferably iodobenzene diacetate.
Preferably, the molar ratio of the allylboron compound, the hypervalent iodine oxidizer and the selenium catalyst is 1:1 to 6:0.1 to 0.5, more preferably 1:2 to 5:0.1 to 0.25, for example 1:1:0.1,1:2:0.1,1:3:0.1,1:4:0.1,1:5:0.1,1:5:0.2,1:5:0.25,1:5:0.3,1: 5:0.5,1: 5:0.5, etc.
Preferably, the molar ratio of the allylboron compound to the sulfonamide or amine sulfonate is 1:1 to 3, more preferably 1: 1-2, for example 1:1,1:1.5,1:2,1:2.5,1:3, etc.
Preferably, the temperature of the reaction is 10 to 60 ℃, more preferably 20 to 60 ℃, still more preferably 25 to 35 ℃, for example 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, etc.
Preferably, the reaction time is not controlled in the reaction process, and the reaction is finished until the system is not changed any more. Typically, the reaction is completed for a period of time less than or equal to 24 hours, such as about 10 hours, 12 hours, 15 hours, 20 hours, 24 hours, etc.
Preferably, the reaction is carried out in a solvent which is sufficient to dissolve or disperse the reactants and which does not participate in the reaction or hinder the reaction. More preferably, the solvent comprises any one or two of dichloromethane, acetone or acetonitrile; still preferably, the solvent is methylene chloride.
Preferably, the amount of the solvent may be appropriately selected according to actual needs. As an example, the ratio of allylboron compound to solvent is 1mmol: 5-20 mL, preferably 1mmol: 8-12 mL.
Preferably, the reaction further comprises a post-treatment step after completion, said post-treatment step comprising purification. The purification method comprises silica gel column chromatography.
Preferably, the yield of the propargyl alpha-aminoborate compound is not less than 40%, more preferably not less than 45%, still more preferably not less than 60%, not less than 65%, not less than 70%, not less than 75%, not less than 80%, not less than 85% and the like.
The invention also provides application of the preparation method of the alpha-amino boron-based compound in preparation of fluorescent tracers, carbohydrate sensors and biological medicines. The alpha-amino boron-based compound has wide application in fluorescent tracers, carbohydrate sensors and biological medicines, so that the preparation method can be applied to the preparation of the fluorescent tracers, the carbohydrate sensors and the biological medicines.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel preparation method of an alpha-amino boron-like compound, which has wide substrate applicability and can prepare various alpha-amino boron-like compounds; meanwhile, the initial raw materials do not need to be subjected to any other treatment and modification, can be directly used for reaction, and have few reaction steps and simple process; the method has the advantages of mild reaction conditions, no need of high temperature or high pressure, no need of acid or alkali additives, simple post-treatment and high efficiency in synthesizing the alpha-amino boron-like compound.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
EXAMPLE 1 Synthesis of Compound 5aa
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (IMeSe, other examples employing the same catalyst) (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) in 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃for 24 hours (the reaction time was the same in each of the other examples). After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 86 percent.
Compound 5aa is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfofamate, having the structure shown below:
Nuclear magnetic resonance and high resolution characterization of compound 5aa was performed as follows:
1 h NMR (500 MHz, acetone-d) 6 )δ6.94(d,J＝9.0Hz,1H),5.72(dt,J＝15.5,6.5Hz,1H),5.60(ddd,J＝15.5,8.0,1.5Hz,1H),4.69(q,J＝11.5Hz,2H),4.29(dd,J＝17.0,7.5Hz,2H),4.10(dd,J＝41.5,17.0Hz,2H),3.73(t,J＝8.5Hz,1H),3.29(s,3H),2.09–2.02(m,2H),1.39–1.32(m,4H),0.87(t,J＝7.0Hz,3H).
13 C NMR (125 MHz, acetone-d) 6 )δ168.4,133.1,128.7,95.0,78.8,63.7,63.5,46.7,22.9,14.2.
ESI-MS:calculated C 14 H 22 BCl 3 N 2 O 7 S[M+Na] + ,501.0199；Found 501.0207.
EXAMPLE 2 Synthesis of Compound 5ab
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trifluoromethyl sulfonamide (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube is sealedSealing, introducing argon, and stirring the reaction solution at 35 ℃ to react. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 80 percent.
Compound 5ab is:
(E) -1, 1-trifluoro-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) methanesulfonic acid having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ab was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.75(d,J＝8.1Hz,1H),5.69(dt,J＝15.3,6.6Hz,1H),5.57(ddt,J＝15.5,7.6,1.3Hz,1H),4.33(dd,J＝17.0,5.8Hz,2H),4.13(dd,J＝33.0,17.0Hz,2H),3.93–3.79(m,1H),3.31(s,3H),2.07–2.04(m,2H),1.39–1.29(m,4H),0.89(t,J＝7.1Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.3,168.1,132.6,128.4,120.7(q,J＝322.1Hz),63.7,63.7,46.8,32.8,32.2,22.7,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
19 F NMR (376 MHz, acetone-d) 6 )δ-77.6.
ESI-MS:calculated C 13 H 20 BF 3 N 2 O 6 S[M+Na] + ,423.0979；Found 423.0981.
Implementation of the synthesis of Compound 5ac of EXAMPLE 3
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order (0.2 mmol,1.0 equiv), p-bromobenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzenediacetic acid (1.0 mmol,5.0 equiv), 2.0mL of di-And a chloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 50 percent.
Compound 5ac is:
(E) -4-bromo-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ac was performed as follows:
1 h NMR (500 MHz, acetone-d) 6 )δ7.80(d,J＝8.0Hz,2H),7.72(d,J＝8.0Hz,2H),6.44(d,J＝10.0Hz,1H),5.14–5.01(m,2H),4.27(dd,J＝17.0,10.5Hz,2H),4.09(dd,J＝41.5,17.0Hz,2H),3.69–3.58(m,1H),3.36(s,3H),1.63(q,J＝7.0Hz,2H),1.18–1.12(m,2H),1.01–0.95(m,2H),0.84(t,J＝7.5Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.6,168.4,142.6,132.7,132.6,131.5,130.3,130.3,127.5,127.1,63.7,63.5,46.4,32.6,31.8,22.9,14.3.
11 B NMR (128 MHz, acetonitrile-d) 3 )δ10.3.
ESI-MS:calculated C 18 H 24 BBrN 2 O 6 S[M+Na] + ,509.0524；Found 509.0527.
Implementation of the Synthesis of Compound 5ad from Extra 4
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), phenylsulfonic acid amine (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. Sealing the reaction tube, and introducingArgon, the reaction mixture was stirred at 35 ℃. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 78%.
Compound 5ad is:
phenyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfomate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ad was performed as follows:
1 h NMR (500 MHz, acetone-d) 6 )δ7.31–7.26(m,3H),7.20–7.14(m,4H),6.87(d,J＝8.8Hz,1H),5.62–5.51(m,1H),5.45(dd,J＝15.4,7.9Hz,1H),4.19–4.10(m,3H),3.93(ddd,J＝85.4,16.9,1.8Hz,3H),3.70(t,J＝8.2Hz,1H),3.13(d,J＝1.8Hz,3H),1.94–1.87(m,3H),1.23–1.15(m,5H),0.71(d,J＝6.6Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.5,168.3,151.8,132.5,130.4,128.9,127.0,122.5,63.7,63.6,46.6,32.8,32.1,22.7,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 18 H 25 BN 2 O 7 S[M+Na] + ,447.1368；Found 447.1364.
EXAMPLE 5 Synthesis of Compound 5ae
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), p-fluorobenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. Junction to be reactedThe reaction solution after the beam is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 72 percent.
Compound 5ae is:
(E) -4-fluoro-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 3ae was performed as follows:
1 h NMR (400 MHz, acetone-d) 6 )δ8.02–7.88(m,2H),7.32(t,J＝8.8Hz,2H),6.37(d,J＝10.0Hz,1H),5.22–5.01(m,2H),4.28(dd,J＝16.8,9.2Hz,2H),4.10(dd,J＝34.8,16.8Hz,2H),3.71–3.56(m,1H),3.36(s,3H),1.68–1.63(m,2H),1.20–1.11(m,2H),1.09–0.95(m,2H),0.83(t,J＝7.2Hz,3H).
13 C NMR (125 MHz, acetone-d) 6 )δ168.6,168.3,166.6,δ165.6(d,J＝250.7Hz),139.7(d,J＝3.0Hz),131.4,131.3,127.7,116.6,116.4,63.7,63.5,46.4,32.7,31.9,22.8,14.1.
11 B NMR (160 MHz, acetone-d) 6 )δ10.5.
19 F NMR (376 MHz, acetone-d) 6 )δ-109.1.
ESI-MS:calculated C 18 H 24 BFN 2 O 6 S[M+Na] + ,449.1324；Found 449.1321.
EXAMPLE 6 Synthesis of Compound 5af
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) benzenesulfonamide (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. Sealing the reaction tubeArgon is introduced, and the reaction liquid is stirred at 35 ℃ to react. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 66 percent.
Compound 5af is:
(E) -N- (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
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nuclear magnetic resonance and high resolution characterization of compound 5af was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.90–7.83(m,2H),7.61–7.48(m,3H),6.30(d,J＝10.0Hz,1H),5.16–4.92(m,2H),4.26(dd,J＝16.8,8.1Hz,2H),4.08(dd,J＝33.6,16.9Hz,2H),3.64(dd,J＝9.8,6.6Hz,1H),3.35(s,3H),1.66–1.46(m,2H),1.18–1.03(m,2H),1.04–0.92(m,2H),0.80(t,J＝7.3Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.7,168.4,143.4,132.9,131.3,129.5,128.3,127.6,63.7,63.5,46.4,32.6,31.8,22.8,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 18 H 25 BN 2 O 6 S[M+Na] + ,431.1419；Found 431.1412.
EXAMPLE 7 Synthesis of Compound 5ag
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), p-toluenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. Junction to be reacted The reaction solution after the beam is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 81 percent.
Compound 5ag is:
(E) -4-methyl-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ag was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ7.66(d,J＝8.3Hz,2H),7.30(d,J＝8.0Hz,2H),5.51–5.40(m,1H),5.07–4.98(m,1H),4.98–4.90(m,1H),3.98(dd,J＝16.9,11.3Hz,2H),3.87(dd,J＝16.9,11.3Hz,2H),3.56–3.48(m,1H),3.13(s,3H),2.38(s,3H),1.61–1.50(m,2H),0.98(qd,J＝7.3,5.0Hz,2H),0.72(t,J＝7.3Hz,3H).
13 C NMR(101MHz,CD 3 CN)δ168.5,168.2,143.8,139.3,131.3,129.9,128.0,127.9,126.9,63.3,63.2,46.2,34.5,22.3,21.0,13.5.
11 B NMR(128MHz,CD 3 CN)δ10.3.
ESI-MS:calculated C 19 H 27 BN 2 O 6 S[M+Na] + ,445.1575；Found 445.1576.
EXAMPLE 8 Synthesis of Compound 5ah
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), p-chlorobenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate and is rotated in vacuumThe solvent was dried and purified by silica gel column chromatography to give the product as a white solid in 76% yield.
Compound 5ah is:
(E) -4-chloro-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
Nuclear magnetic resonance and high resolution characterization of compound 5ah was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.92–7.82(m,2H),7.61–7.50(m,2H),6.42(d,J＝10.4Hz,0H),5.10(q,J＝6.0Hz,2H),4.27(dd,J＝17.2,9.2Hz,2H),4.15–3.98(m,2H),3.63(d,J＝7.2Hz,1H),3.36(d,J＝9.2Hz,3H),1.70–1.55(m,2H),1.66-1.61(m,2H),1.06–0.94(m,2H),0.83(t,J＝7.6Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.6,168.3,142.2,138.6,131.5,130.3,129.7,127.5,63.7,63.5,46.4,32.7,31.9,22.9,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.29.
ESI-MS:calculated C 18 H 24 BClN 2 O 6 S[M+Na] + ,465.1029；Found 465.1031.
EXAMPLE 9 Synthesis of Compound 5ai
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), 4-tert-butylbenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. Diluting the reaction solution with ethyl acetate after the reaction is finished, spin-drying the solvent in vacuum, and purifying with silica gel column chromatography to obtain the product which is whiteThe yield of the coloured solid was 76%.
Compound 5ai is:
(E) -4- (tert-butyl) -N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ai was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.8(d,J＝8.6Hz,2H),7.6(d,J＝8.5Hz,2H),6.2(d,J＝10.1Hz,1H),5.2–5.0(m,2H),4.3(dd,J＝16.8,10.1Hz,2H),4.1(dd,J＝35.8,16.8Hz,2H),3.7–3.5(m,1H),3.3(s,3H),1.6(q,J＝6.7,5.8Hz,2H),1.4(s,9H),1.2–1.1(m,3H),1.1–1.0(m,2H),0.8(t,J＝7.3Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.7,168.3,156.3,140.5,131.2,128.3,127.5,126.4,63.7,63.5,46.4,35.6,32.6,31.7,31.4,31.4,22.9,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.38.
ESI-MS:calculated C 22 H 33 BN 2 O 6 S[M+Na] + ,487.2045；Found 487.2040
EXAMPLE 10 Synthesis of Compound 5aj
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order (0.2 mmol,1.0 equiv), p-methoxybenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 60 percent.
Compound 5aj is:
(E) -4-methoxy-N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) benzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5aj was performed as follows:
1 h NMR (500 MHz, acetonitrile-d) 3 )δ7.7(d,J＝8.9Hz,2H),7.0(d,J＝8.9Hz,2H),5.4(d,J＝10.3Hz,1H),5.1–5.0(m,1H),5.0–4.9(m,1H),4.0(dd,J＝16.9,13.7Hz,3H),3.9–3.9(m,2H),3.8(s,4H),3.5–3.5(m,1H),3.1(s,3H),1.6–1.6(m,2H),1.2–1.1(m,2H),1.0–0.9(m,2H),0.8(t,J＝7.3Hz,3H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ169.0,168.6,163.8,134.4,132.0,131.1,130.5,128.4,127.3,114.9,63.8,63.6,56.4,46.6,32.7,31.9,23.0,14.2.
11 B NMR (128 MHz, acetonitrile-d) 3 )δ10.7.
ESI-MS:calculated C 19 H 27 BN 2 O 7 S[M+Na] + ,461.1524；Found 461.1529.
EXAMPLE 11 Synthesis of Compound 5ak
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) methylsulfonamide (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 56%.
Compound 5ak is:
(E) -N- (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborolan-2-yl) hept-2-en-1-yl) methanesulfonyl, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ak was performed as follows:
1 h NMR (500 MHz, acetonitrile-d) 3 )δ5.63(dtd,J＝15.5,6.8,1.0Hz,1H),5.48(ddt,J＝15.5,8.3,1.4Hz,1H),5.14(d,J＝10.3Hz,1H),3.98(dd,J＝16.9,3.5Hz,2H),3.85(dd,J＝16.9,9.1Hz,2H),3.57(t,J＝9.3Hz,1H),3.07(s,3H),2.84(s,3H),2.07(q,J＝6.6Hz,2H),1.40–1.32(m,4H),0.90(t,J＝7.1Hz,3H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ168.9,168.6,133.1,129.2,63.8,63.7,46.7,42.5,32.8,32.3,22.9,14.2.
11 B NMR (128 MHz, acetonitrile-d) 3 )δ10.4.
ESI-MS:calculated C 13 H 23 BN 2 O 6 S[M+Na] + ,369.1262；Found 369.1260.
EXAMPLE 12 Synthesis of Compound 5al
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), p-nitrobenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 79 percent.
Compound 5al is:
(E) -N- (1- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) -4-nitrobenzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5al was performed, with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ8.41(d,J＝8.6Hz,2H),8.15(d,J＝8.6Hz,2H),6.73(d,J＝10.4Hz,1H),5.26–4.97(m,2H),4.29(dd,J＝16.8,5.6Hz,2H),4.11(dd,J＝32.4,16.8Hz,2H),3.73(t,J＝8.4Hz,1H),3.37(d,J＝9.2Hz,3H),1.59(q,J＝6.8Hz,2H),1.15–0.98(m,2H),0.98–0.81(m,2H),0.75(t,J＝7.2Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.5,168.3,150.8,149.2,131.8,130.0,127.6,124.9,63.7,63.6,46.6,32.5,31.9,22.8,14.0.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 18 H 24 BN 3 O 8 S[M+Na] + ,476.1269；Found 476.1274.
EXAMPLE 13 Synthesis of Compound 5am
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) p-cyanobenzenesulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 61%.
Compound 5am is:
4-cyanophenyl (E) - (1- (6-methyl-4, 8-dio-1, 3,6, 2-dioxaborolan-2-yl) hept-2-en-1-yl) sulfomate, having the structural formula:
nuclear magnetic resonance and high resolution characterization of compound 5am was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.95–7.82(m,2H),7.51(dd,J＝9.0,2.3Hz,2H),7.34(d,J＝8.8Hz,1H),5.75–5.61(m,1H),5.53(dd,J＝15.6,8.2Hz,1H),4.30(dd,J＝16.9,7.5Hz,2H),4.10(dd,J＝45.8,17.0Hz,2H),3.84(d,J＝7.1Hz,1H),3.32(d,J＝9.8Hz,3H),2.03–1.97(m,2H),1.29(p,J＝3.6Hz,4H),0.83(q,J＝5.2,3.5Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.3,155.0,134.9,133.0,128.6,128.6,123.4,123.2,118.7,110.6,63.8,63.6,46.7,32.8,32.1,22.8,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.7.
ESI-MS:calculated C 19 H 24 BN 3 O 7 S[M+Na] + ,472.1320；Found 472.1318.
EXAMPLE 14 Synthesis of Compound 5ao
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), p-methoxybenzenesulfonamine (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 78%.
Compound 5ao is:
4-methoxyphenyl (E) - (1- (6-methyl-4, 8-dio-1, 3,6, 2-dioxaborolan-2-yl) hept-2-en-1-yl) sulfomate, having the structural formula:
nuclear magnetic resonance and high resolution characterization of compound 5ao was performed as follows:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ7.19(d,J＝9.1Hz,2H),6.93(d,J＝9.1Hz,2H),5.95(d,J＝9.1Hz,1H),5.71–5.59(m,1H),5.48(ddd,J＝15.5,8.4,1.5Hz,1H),3.98(dd,J＝17.0,3.0Hz,2H),3.89–3.79(m,2H),3.73(d,J＝8.6Hz,1H),2.99(s,3H),2.05(p,J＝6.1,5.5Hz,2H),1.30(td,J＝8.8,8.2,4.4Hz,5H),0.89–0.81(m,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.5,168.3,158.8,145.1,132.5,129.1,129.1,123.8,115.2,115.2,63.8,63.6,62.9,55.9,46.6,32.9,32.2,22.7,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 19 H 27 BN 2 O 8 S[M+Na] + ,477.1473；Found 477.1472.
EXAMPLE 15 Synthesis of Compound 5ap
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), 4-methyl ester benzenesulfonamine (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 67 percent.
Compound 5ap was:
methyl (E) -4- ((N- (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfonyl) oxy) benzoate has the structural formula shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ap was performed with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ8.12–7.98(m,2H),7.49–7.39(m,2H),7.23(d,J＝8.8Hz,1H),5.68(dt,J＝13.9,6.6Hz,1H),5.54(dd,J＝15.5,8.1Hz,1H),4.29(dd,J＝16.9,10.0Hz,2H),4.09(dd,J＝53.2,16.9Hz,3H),3.89(s,3H),3.88–3.80(m,1H),3.30(s,3H),2.04–1.98(m,2H),1.30(q,J＝3.6Hz,4H),0.82(q,J＝5.2,3.4Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.4,168.3,166.4,155.3,132.8,131.9,128.8,128.7,128.7,122.2,63.8,63.6,52.5,46.7,32.9,32.1,22.8,14.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.3.
ESI-MS:calculated C 20 H 27 BN 2 O 9 S[M+Na] + ,505.1423；Found 505.1420.
EXAMPLE 16 Synthesis of Compound 5ar
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), hexafluoroisopropylsulfonic acid amine (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 60 percent.
Compound 5ar is:
1, 3-hexafluoropopan-2-yl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfofamate, having the structural formula shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ar was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.40(d,J＝8.8Hz,1H),5.72–5.49(m,2H),5.49–5.37(m,1H),4.01(dd,J＝17.1,2.1Hz,2H),3.86(dd,J＝17.1,6.3Hz,2H),3.68(t,J＝8.5Hz,1H),3.01(s,3H),2.04(p,J＝6.2,5.5Hz,2H),1.40–1.27(m,4H),0.89(t,J＝7.1Hz,3H).
13 C NMR (126 MHz, acetone) δ 168.3,168.3,132.9,128.1, δ 121.58 (q, j=281.7 Hz), 72.62 (dt, j=69.0, 34.4 Hz), 63.8,63.7,46.7,32.9,32.0,22.8,14.2.
11 B NMR (160 MHz, acetone) delta 10.5.
ESI-MS:calculated C 15 H 21 BF 6 N 2 O 7 S[M+Na] + ,521.0959；Found 521.0954.
EXAMPLE 17 Synthesis of Compound 5as
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order (0.2 mmol,1.0 equiv), amine triflate (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 64 percent.
Compound 5as is:
2,2-trifluoroethyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfofamate, the structural formula of which is shown as follows:
nuclear magnetic resonance and high resolution characterization of compound 5as was performed, with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ6.94(d,J＝9.3Hz,1H),5.77–5.65(m,1H),5.57(ddt,J＝15.4,8.2,1.3Hz,1H),4.63–4.49(m,2H),4.30(dd,J＝17.0,5.1Hz,2H),4.11(dd,J＝32.3,17.0Hz,2H),3.69(t,J＝8.7Hz,1H),3.28(s,3H),2.05(td,J＝5.4,4.5,3.1Hz,2H),1.39–1.28(m,4H),0.89(t,J＝7.0Hz,3H).
13 C NMR (126 MHz, acetone) δ 168.5,168.4,133.3,128.5,123.78 (q, j= 276.8 Hz), 65.31 (q, j=36.8 Hz), 63.7,63.6,46.7,32.8,32.1,22.8,14.2.
11 B NMR (160 MHz, acetone) δ10.6.
ESI-MS:calculated C 14 H 22 BF 3 N 2 O 7 S[M+Na] + ,453.1085；Found 453.1084.
EXAMPLE 18 Synthesis of Compound 5at
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv), o-nitrobenzenesulfonamide (0.4 mmol,2.0 equiv), selenium catalyst (0.05 mmol,0.25 equiv), iodobenzene diacetic acid (1.0 mmol,5.0 equiv), 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 59 percent.
Compound 5at is:
(E) -N- (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) -2-nitrobenzenesulfonamide having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5at was performed, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ8.04–7.95(m,1H),7.88–7.70(m,3H),5.63(d,J＝10.2Hz,1H),5.32–5.18(m,1H),5.09(ddt,J＝15.6,8.3,1.5Hz,1H),4.03(dd,J＝17.1,5.7Hz,2H),3.91(dd,J＝17.1,3.3Hz,2H),3.78–3.70(m,1H),3.11(s,3H),1.66–1.53(m,2H),1.12–1.00(m,2H),0.94–0.84(m,2H),0.78(t,J＝7.3Hz,3H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ168.8,168.6,148.8,135.3,134.9,133.7,133.3,132.1,132.1,127.0,125.8,63.8,63.7,47.1,32.4,31.7,22.8,14.1.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.4.
ESI-MS:calculated C 18 H 24 BN 3 O 8 S[M+Na] + ,476.1269；Found 476.1262.
EXAMPLE 19 Synthesis of Compound 5ba
Sequentially adding (E) -7- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-5-en-1-yl 4-methoxybenzoate into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 59 percent.
Compound 5ba is:
(E) -7- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborolan-2-yl) -7- (((2, 2-trichloroethoxy) sulfoyl) amino) hept-5-en-1-yl 4-methoxybenzoate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ba was performed with the following results:
1 H NMR (400 MHz, acetonitrile-d) 3 )δ8.05–7.87(m,2H),7.05–6.90(m,2H),6.08(d,J＝9.4Hz,1H),5.70(dt,J＝15.5,6.6Hz,1H),5.55(dd,J＝15.5,8.2Hz,1H),4.62(q,J＝11.2Hz,2H),4.25(t,J＝6.5Hz,2H),4.01(dd,J＝17.1,2.4Hz,2H),3.89(d,J＝3.1Hz,1H),3.85(s,4H),3.66(t,J＝8.7Hz,1H),3.04(s,3H),2.13(q,J＝7.3Hz,2H),1.79–1.72(m,2H),1.60–1.45(m,2H).
13 C NMR(126MHz,CD 3 CN)δ168.6,166.9,164.4,133.4,132.3,128.8,123.8,114.8,94.8,78.9,65.3,63.8,63.7,56.3,47.0,32.8,29.1,26.5.
11 B NMR(160MHz,CD 3 CN)δ10.60.
ESI-MS:calculated C 22 H 28 BCl 3 N 2 O 10 S[M+Na] + ,651.0516；Found 651.0518.
EXAMPLE 20 Synthesis of Compound 5bb
(E) -2- (hex-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in sequence(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid, and the yield is 78%.
Compound 5bb is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hex-2-en-1-yl) sulfamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bb was performed with the following results:
1 h NMR (500 MHz, acetone-d) 6 )δ6.96(d,J＝9.0Hz,1H),5.73(dt,J＝14.0,6.5Hz,1H),5.62(dd,J＝15.5,8.0Hz,1H),4.75–4.68(m,2H),4.37–4.26(m,2H),4.12(dd,J＝42.0,17.0,Hz,2H),3.75(t,J＝8.5Hz,1H),3.31(s,3H),2.10–2.07(m,1H),2.05–2.02(m,1H),1.44–1.35(m,2H),0.91(t,J＝7.5Hz,3H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.4,168.3,132.9,129.0,95.1,78.8,63.7,63.6,46.7,35.4,23.1,14.0.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 13 H 20 BCl 3 N 2 O 7 S[M+Na] + ,487.0042；Found 487.0042.
EXAMPLE 21 Synthesis of Compound 5bc
(E) -6-methyl-2- (tridec-2-en-1-yl) -1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid, and the yield is 66%.
Compound 6bc is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) tridec-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 6c was performed, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.02(d,J＝9.6Hz,1H),5.68(dt,J＝14.0,6.4Hz,1H),5.54–5.48(m,1H),4.70–4.56(m,2H),4.01(d,J＝17.2Hz,2H),3.86(d,J＝17.2Hz,2H),3.64(t,J＝8.8Hz,1H),3.04(s,3H),2.04(t,J＝7.2Hz,2H),1.38–1.19(m,18H),0.89(t,J＝6.4Hz,3H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ168.6,134.0,128.3,94.8,78.9,63.8,63.6,46.9,33.2,32.6,30.3,30.3,30.2,30.1,30.0,23.4,14.4.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.46.
ESI-MS:calculated C 20 H 34 BCl 3 N 2 O 7 S[M+Na] + ,585.1138；Found 585.1141.
EXAMPLE 22 Synthesis of Compound 5bd
(E) -2- (7-chlorohept-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid, and the yield is 66%.
Compound 5bd is:
2,2-trichloroethyl (E) - (7-chloro-1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bd was performed as follows:
1 H NMR (500 MHz, acetonitrile-d) 3 )δ6.03(d,J＝9.5Hz,1H),5.67(dt,J＝15.5,6.5Hz,1H),5.54(dd,J＝15.5,8.0Hz,1H),4.71–4.55(m,2H),4.01(d,J＝17.0Hz,2H),3.87(dd,J＝17.0,4.5Hz,2H),3.65(t,J＝9.0Hz,1H),3.59(t,J＝6.5Hz,2H),3.04(s,3H),2.13–2.03(m,2H),1.80–1.75(m,2H),1.53–1.48(m,2H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ168.5,133.2,128.9,94.8,78.9,63.8,63.7,47.0,46.1,32.9,32.3,27.2.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.24.
ESI-MS:calculated C 14 H 21 BCl 4 N 2 O 7 S[M+Na] + ,534.9809；Found 534.9808.
EXAMPLE 23 Synthesis of Compound 5be
(E) -2- (6- (5, 5-dimethyl-1, 3-dioxan-2-yl) hex-2-en-1-yl) -6-methyl-1,3,6, 2-dioxaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 68 percent.
Compound 5 be:
2,2-trichloroethyl (E) - (6- (5, 5-dimethyl-1, 3-dioxan-2-yl) -1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hex-2-en-1-yl) sulfamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5be was performed, with the following results:
1 h NMR (500 MHz, acetonitrile-d) 3 )δ6.01(d,J＝9.4Hz,1H),5.67(dt,J＝14.0,6.6Hz,1H),5.51(dd,J＝15.5,8.3Hz,1H),4.70–4.55(m,2H),4.41(t,J＝5.0Hz,1H),4.00(d,J＝17.0Hz,2H),3.86(ddd,J＝17.0,4.0Hz,2H),3.64(t,J＝9.0Hz,1H),3.52(d,J＝10.7Hz,2H),3.40(d,J＝10.8Hz,2H),3.04(s,3H),2.08–2.04(m,2H),1.61–1.52(m,2H),1.52–1.39(m,2H),1.11(s,3H),0.68(s,3H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ168.5,133.6,128.7,102.7,94.8,78.9,77.5,63.8,63.7,47.0,35.1,32.9,30.7,24.4,23.2,21.9.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.12.
ESI-MS:calculated C 19 H 30 BCl 3 N 2 O 9 S[M+Na] + ,601.0723；Found 601.0729.
EXAMPLE 24 Synthesis of Compound 5bf
(E) -6-methyl-2- (5-phenacylpent-2-en-1-yl) -1,3,6,2-dioxazaborocane-4,8-dione was sequentially added to the reaction tube (0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 68 percent.
Compound 5 bf:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) -5-phenyl-pent-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bf was performed, with the following results:
1 h NMR (400 MHz, acetone-d) 6 )δ7.30–7.22(m,4H),7.19–7.13(m,1H),6.95(d,J＝9.2Hz,1H),5.80(dt,J＝15.6,6.4Hz,1H),5.67(ddt,J＝15.6,8.0,1.2Hz,1H),4.79–4.67(m,2H),4.28(d,J＝16.8Hz,2H),4.03(dd,J＝16.8,4.4Hz,2H),3.75(t,J＝8.4Hz,1H),3.24(s,3H),2.79–2.67(m,2H),2.42–2.36(m,2H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.4,168.4,142.7,132.6,129.3,129.2,129.1,126.6,95.0,78.8,63.6,63.5,46.6,36.2,35.2.
11 B NMR (160 MHz, acetone-d) 6 )δ10.5.
ESI-MS:calculated C 18 H 22 BCl 3 N 2 O 7 S[M+Na] + ,549.0199；Found 549.0192.
EXAMPLE 25 Synthesis of Compound 5bg
Sequentially adding (E) -7- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-5-en-1-yl pivalate into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 68 percent.
Compound 5bg is:
(E) -7- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborocan-2-yl) -7- (((2, 2-trichloroethoxy) sulfonyl) amino) hept-5-en-1-yl pivalate having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bg was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.03(d,J＝9.2Hz,1H),5.68(dt,J＝15.6,6.4Hz,1H),5.53(dd,J＝15.6,8.0Hz,1H),4.63(q,J＝11.2Hz,2H),4.08–3.94(m,4H),3.86(dd,J＝17.2,2.4Hz,2H),3.65(t,J＝8.8Hz,1H),3.04(s,3H),2.12–2.06(m,2H),1.66–1.59(m,2H),1.51–1.41(m,2H),1.16(s,9H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ179.0,168.6,168.5,133.4,128.8,94.8,78.9,64.9,63.8,63.7,47.0,39.3,32.7,29.0,27.5,27.4,26.4.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.2.
ESI-MS:calculated C 19 H 30 BCl 3 N 2 O 9 S[M+Na] + ,601.0723；Found 601.0728.
EXAMPLE 26 Synthesis of Compound 5bh
To the reaction tube was added ethyl (E) -4- (5- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxaborolan-2-yl) pent-3-en-1-yl) benzoate in sequence(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 68 percent.
Compound 5bh is:
ethylene (E) -4- (5- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborolan-2-yl) -5- (((2, 2-trichloromethod) sulfonyl) amino) pent-3-en-1-yl) benzoate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bh was performed with the following results:
1 H NMR (400 MHz, acetonitrile-d) 3 )δ7.92(d,J＝8.0Hz,2H),7.34(d,J＝8.0Hz,2H),6.04(d,J＝9.2Hz,1H),5.75–5.68(m,1H),5.62–5.51(m,1H),4.62(q,J＝11.2Hz,2H),4.31(q,J＝7.2Hz,2H),3.99(dd,J＝17.2,7.6Hz,2H),3.81(dd,J＝19.6,17.2Hz,2H),3.65(t,J＝8.8Hz,1H),3.00(s,3H),2.77(td,J＝7.6,2.4Hz,2H),2.42–2.36(m,2H),1.34(t,J＝7.2Hz,3H).
13 C NMR (126 MHz, acetonitrile-d) 3 )δ168.6,167.2,148.5,132.7,130.3,129.7,129.3,94.8,78.8,63.7,63.6,61.6,47.0,36.1,34.6,14.6.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.1.
ESI-MS:calculated C 21 H 26 BCl 3 N 2 O 9 S[M+Na] + ,621.0410；Found 621.0415.
EXAMPLE 27 Synthesis of Compound 5bi
(E) -2- (5- (benzoyloxy) pent-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 77 percent.
Compound 5bi is:
2,2-trichloroethyl (E) - (5- (benzoyloxy) -1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) pent-2-en-1-yl) sulfolane, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bi was performed, with the following results:
1 h NMR (500 MHz, acetone-d) 6 )δ7.41–7.31(m,4H),7.31–7.22(m,1H),6.98(d,J＝9.0Hz,1H),5.85–5.75(m,1H),5.70(dd,J＝15.5,8.0Hz,1H),4.78–4.67(m,2H),4.51(s,2H),4.25(dd,J＝17.0,5.0Hz,2H),4.08(dd,J＝26.0,17.0Hz,2H),3.75(t,J＝8.5Hz,1H),3.54(t,J＝6.5Hz,2H),3.26(s,3H),2.37(q,J＝6.5Hz,2H).
13 C NMR (126 MHz, acetone-d) 6 )δ168.4,168.3,139.8,130.6,129.8,129.1,128.4,128.1,95.1,78.8,73.2,70.3,63.6,63.6,46.6,33.8.
11 B NMR (160 MHz, acetone-d) 6 )δ10.4.
ESI-MS:calculated C 19 H 24 BCl 3 N 2 O 8 S[M+Na] + ,579.0304；Found 579.0305.
EXAMPLE 28 Synthesis of Compound 5bj
Sequentially adding (E) -6-methyl-2- (4-phenyl-butyl-2-en-1-yl) -1,3,6, 2-dioxazaborolane-4, 8-dione into a reaction tube (0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 45 percent.
Compound 5bj is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborolan-2-yl) -4-phenylbut-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bj was performed as follows:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ7.35–7.28(m,2H),7.27–7.16(m,3H),6.10(d,J＝9.5Hz,1H),5.84(dtd,J＝15.4,6.7,1.1Hz,1H),5.57(ddt,J＝15.4,8.2,1.5Hz,1H),4.65–4.49(m,2H),4.01(dd,J＝17.0,2.2Hz,2H),3.85(d,J＝17.0Hz,2H),3.70(t,J＝8.9Hz,1H),3.40(d,J＝6.7Hz,3H),3.03(s,3H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ168.6,168.6,141.3,132.3,129.8,129.5,129.5,127.0,94.8,78.9,63.8,63.6,47.0,39.3.
11 B NMR (128 MHz, acetonitrile-d) 3 )δ10.26.
ESI-MS:calculated C 17 H 20 BCl 3 N 2 O 7 S[M+Na] + ,535.0042；Found 535.0040.
EXAMPLE 29 Synthesis of Compound 5bk
Sequentially adding (E) -6-methyl-2- (4- (naphthalen-1-yl) but-2-en-1-yl) -1,3,6, 2-dioxazaborolane-4, 8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 51 percent.
Compound 5bk is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborolan-2-yl) -4- (naphthalen-1-yl) but-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bk was performed, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ8.15–8.06(m,1H),7.93–7.86(m,1H),7.77(dd,J＝7.3,1.9Hz,1H),7.60–7.47(m,2H),7.48–7.38(m,2H),6.07(d,J＝9.5Hz,1H),6.00(dtd,J＝15.4,6.5,0.9Hz,1H),5.62(ddt,J＝15.5,8.1,1.6Hz,1H),4.58–4.41(m,2H),3.97(dd,J＝17.1,5.0Hz,2H),3.86(t,J＝5.2Hz,2H),3.79(dd,J＝17.1,9.9Hz,2H),3.71(t,J＝8.8Hz,1H),2.98(s,3H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ168.5,137.5,134.9,132.7,131.6,130.1,129.6,127.8,127.3,127.0,126.8,126.7,125.0,94.8,78.8,63.7,63.6,46.9,36.5.
11 B NMR (128 MHz, acetonitrile-d) 3 )δ10.28.
ESI-MS:calculated C 21 H 22 BCl 3 N 2 O 7 S[M+Na] + ,585.0199；Found 585.0193.
EXAMPLE 30 Synthesis of Compound 5bl
Sequentially adding (E) -2- (3-cyclohexyalyl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 80 percent.
Compound 5bl is:
2,2-trichloroethyl (E) - (3-cyclohexyl-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) all) sulfamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bl was performed, with the following results:
1 H NMR (400 MHz, acetonitrile-d) 3 )δ6.00(d,J＝9.2Hz,1H),5.64(dd,J＝15.7,6.5Hz,1H),5.47(ddd,J＝15.6,8.2,1.2Hz,1H),4.63(q,J＝11.3Hz,2H),4.00(dd,J＝17.0,3.2Hz,2H),3.85(dd,J＝17.1,2.3Hz,2H),3.63(t,J＝8.7Hz,1H),3.03(s,3H),1.77–1.59(m,5H),1.36–1.02(m,6H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ168.6,168.5,139.5,126.1,94.8,78.9,63.8,63.7,46.9,41.3,33.6,33.6,26.9,26.7.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.23.
ESI-MS:calculated C 16 H 24 BCl 3 N 2 O 7 S[M+Na] + ,527.0355；Found 527.0353.
EXAMPLE 31 Synthesis of Compound 5bm
(E) -2- (hepta-2, 6-dien-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is a pale yellow solid with the yield of 76%.
Compound 5bm is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hepta-2, 6-dien-1-yl) sulfomate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bm gave the following results:
1 h NMR (500 MHz, acetone-d) 6 )δ6.96(d,J＝9.1Hz,1H),5.93–5.81(m,1H),5.81–5.70(m,1H),5.65(dd,J＝15.5,8.1Hz,1H),5.07–4.88(m,2H),4.78–4.66(m,2H),4.31(dd,J＝17.0,8.1Hz,2H),4.12(dd,J＝40.3,17.0Hz,2H),3.75(t,J＝8.3Hz,1H),3.31(s,3H),2.22–2.08(m,3H).
13 C NMR(101MHz,CD 3 CN)δ168.6,139.4,133.1,128.9,115.4,94.8,78.9,63.8,63.7,47.0,34.0,32.6.
11 B NMR(128MHz,CD 3 CN)δ10.4.
ESI-MS:calculated C 14 H 20 BCl 3 N 2 O 7 S[M+Na] + ,499.0042；Found 499.0046.
EXAMPLE 32 Synthesis of Compound 5bn
Sequentially adding (E) -7- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-5-en-1-yl benzoate into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid, and the yield is 78%.
Compound 5bn is:
(E) -7- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborocan-2-yl) -7- (((2, 2-trichloroethoxy) sulfonyl) amino) hept-5-en-1-yl benzoate having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bn was performed as follows:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ8.01(dd,J＝8.1,1.4Hz,2H),7.68–7.55(m,1H),7.49(t,J＝7.6Hz,2H),6.11(d,J＝9.1Hz,1H),5.70(dt,J＝15.5,6.5Hz,1H),5.65–5.48(m,1H),4.62(q,J＝11.2Hz,2H),4.29(t,J＝6.5Hz,2H),4.02(dd,J＝17.0,2.5Hz,2H),3.87(dd,J＝17.1,3.1Hz,2H),3.66(t,J＝8.6Hz,1H),3.05(s,3H),2.18–2.06(m,2H),1.83–1.71(m,2H),1.63–1.45(m,2H).
13 C NMR(126MHz,CD 3 CN)δ168.7,168.6,167.2,133.9,133.4,131.5,130.2,129.5,129.5,128.8,94.8,78.9,65.7,63.8,63.7,47.0,32.7,29.0,26.5.
11 B NMR(160MHz,CD 3 CN)δ10.17.
ESI-MS:calculated C 21 H 26 BCl 3 N 2 O 9 S[M+Na] + ,621.0410；Found 621.0413.
EXAMPLE 33 Synthesis of Compound 5bo
(E) -2- (5- (4- (tert-butyl) phenyl) -4-methylpent-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 67 percent.
Compound 5bo is:
2,2-trichloroethyl (E) - (5- (4- (tert-butyl) phenyl) -4-methyl-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) pent-2-en-1-yl) sulfoamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bo was performed with the following results:
1 H NMR (400 MHz, acetonitrile-d) 3 )δ7.39–7.28(m,2H),7.22–7.10(m,2H),6.00(dd,J＝14.0,8.8Hz,1H),5.77–5.60(m,1H),5.55–5.42(m,1H),4.72–4.33(m,2H),4.03–3.39(m,5H),2.94(s,3H),2.74–2.58(m,1H),2.58–2.41(m,2H),1.29(s,9H),0.96(d,J＝6.3Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ168.6,168.5,168.4,149.6,149.6,139.6,138.9,138.7,138.6,129.9,129.8,127.0,126.7,126.2,126.1,94.9,94.8,78.9,78.9,63.7,63.7,63.6,63.5,46.9,46.8,43.2,43.1,39.0,38.6,35.0,34.9,31.7,20.3,19.7.
ESI-MS:calculated C 23 H 32 BCl 3 N 2 O 7 S[M+Na] + ,619.0981；Found 619.0974.
EXAMPLE 34 Synthesis of 5bp Compound
(E) -2- (but-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 59 percent.
The compound 5bp is:
2,2-trichloroethyl (E) - (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborolan-2-yl) but-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization were performed on compound 5bp, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.02(d,J＝9.6Hz,1H),5.68(dq,J＝15.6,6.4Hz,1H),5.53(dd,J＝15.4,8.5Hz,1H),4.61(q,J＝11.1Hz,2H),4.00(dd,J＝17.1,2.5Hz,2H),3.87(dd,J＝17.0,3.6Hz,2H),3.63(t,J＝9.0Hz,1H),3.04(s,3H),1.70(d,J＝6.3Hz,3H).
13 C NMR (101 MHz, acetonitrile-d) 3 )δ168.6,129.7,128.8,94.7,78.8,63.8,63.7,47.0,18.2.
11 B NMR (160 MHz, acetonitrile-d) 3 )δ10.52.
ESI-MS:calculated C 11 H 16 BCl 3 N 2 O 7 S[M+Na] + ,458.9729；Found 458.9726.
EXAMPLE 35 Synthesis of Compound 5bq
Sequentially adding tert-butyl (E) -5- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) pent-3-enoate into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 58 percent.
Compound 5bq is:
tert-butyl (E) -5- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborolan-2-yl) -5- (((2, 2-trichloroethoxy) sulfocarbonyl) amino) pent-3-enoate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bq was performed as follows:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.20(d,J＝9.4Hz,1H),5.73(dt,J＝15.9,6.5Hz,1H),5.68–5.57(m,1H),4.68(d,J＝1.3Hz,2H),4.07–3.96(m,2H),3.89(ddd,J＝17.0,5.1,1.3Hz,2H),3.70(t,J＝8.6Hz,1H),3.05(s,3H),3.00(d,J＝6.5Hz,2H),1.43(d,J＝1.3Hz,9H).
13 C NMR(126MHz,CD 3 CN)δ171.9,168.6,168.6,132.2,125.7,94.9,81.3,78.9,63.8,63.7,47.0,39.3,28.3,28.3.
11 B NMR(128MHz,CD 3 CN)δ10.09.
ESI-MS:calculated C 16 H 24 BCl 3 N 2 O 9 S[M+Na] + ,559.0253；Found 559.0252.
EXAMPLE 36 Synthesis of Compound 5br
To the reaction tube was added tert-butyl (E) -4- (5- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) pent-3-en-1-yl) piperidine-1-carbox-ylate in sequence(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 62 percent.
Compound 5br is:
tert-butyl (E) -4- (5- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborolan-2-yl) -5- (((2, 2-trichloromethod) sulfonyl) amino) pent-3-en-1-yl) piperidine-1-carbox-ylate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5br was performed with the following results:
1 H NMR (400 MHz, acetonitrile-d) 3 )δ6.03(d,J＝9.4Hz,1H),5.67(dt,J＝14.1,6.5Hz,1H),5.52(dd,J＝15.6,8.3Hz,1H),4.63(qd,J＝11.3,1.4Hz,2H),4.05–3.93(m,4H),3.87(dt,J＝17.0,2.0Hz,2H),3.64(t,J＝8.8Hz,1H),3.04(s,3H),2.77–2.58(m,2H),2.09(q,J＝7.4Hz,2H),1.65(d,J＝13.1Hz,2H),1.41(s,9H),1.31(dt,J＝13.2,6.7Hz,3H),1.04–0.97(m,2H).
13 C NMR(101MHz,CD 3 CN)δ168.6,155.5,133.8,128.6,94.8,79.5,78.9,63.8,63.7,47.0,36.6,36.1,33.0,32.8,30.2,28.6.
ESI-MS:calculated C 22 H 35 BCl 3 N 3 O 9 S[M+Na] + ,656.1145；Found 656.1141.
EXAMPLE 37 Synthesis of Compound 5bs
Sequentially adding ethyl (E) -7- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hept-5-enoate into a reaction tube
(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 82 percent.
Compound 5bs was:
ethylene (E) -7- (6-methyl-4, 8-dio-1, 3,6, 2-dioxazaborolan-2-yl) -7- (((2, 2-trichloroethoxy) sulfo-amino) hept-5-enoate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bs was performed, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.07(d,J＝9.4Hz,1H),5.70–5.59(m,1H),5.54(ddt,J＝15.5,8.1,1.3Hz,1H),4.70–4.57(m,2H),4.07(q,J＝7.1Hz,2H),4.02(dd,J＝17.1,2.3Hz,2H),3.87(dd,J＝17.0,4.5Hz,2H),3.66(t,J＝8.7Hz,1H),3.05(s,3H),2.28(t,J＝7.6Hz,2H),2.08(qd,J＝7.1,2.7Hz,3H),1.70–1.63(m,2H),1.20(t,J＝7.1Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ174.2,168.7,168.6,132.7,129.3,94.8,78.9,63.8,63.7,60.9,47.0,34.2,32.4,25.3,14.6.
11 B NMR(128MHz,CD 3 CN)δ10.18.
ESI-MS:calculated C 16 H 24 BCl 3 N 2 O 9 S[M+Na] + ,559.0253；Found 559.0252.
EXAMPLE 38 Synthesis of Compound 5bt
Sequentially adding (E) -2- (3-cyclopolylalyl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 81 percent.
Compound 5bt is:
2,2-trichloroethyl (E) - (3-cyclyl-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) all) sulfamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bt resulted in the following:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ5.93(d,J＝9.3Hz,1H),5.59(ddd,J＝15.5,7.5,0.8Hz,1H),5.43(ddd,J＝15.5,8.2,1.0Hz,1H),4.55(q,J＝11.2Hz,2H),3.93(dd,J＝17.0,2.7Hz,2H),3.77(dd,J＝17.0,1.4Hz,2H),3.55(t,J＝8.8Hz,1H),2.96(s,3H),2.48–2.29(m,1H),1.77–1.64(m,2H),1.64–1.53(m,2H),1.48(ddt,J＝7.6,4.3,2.1Hz,2H),1.27–1.16(m,2H).
13 C NMR(101MHz,CD 3 CN)δ168.6,168.6,138.3,126.7,94.9,79.0,63.8,63.7,46.9,44.0,33.7,33.7,25.8,25.8.
11 B NMR(128MHz,CD 3 CN)δ10.2.
ESI-MS:calculated C 15 H 22 BCl 3 N 2 O 7 S[M+Na] + ,513.0199；Found 513.0205.
EXAMPLE 39 Synthesis of Compound 5bu
(E) -2- (9- (benzoyloxy) non-2-en-1-yl) -6-methyl-1,3,6, 2-dioxaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 78%.
Compound 5bu is:
2,2-trichloroethyl (E) - (9- (benzoyloxy) -1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) non-2-en-1-yl) sulfofamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5bu was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ7.45–7.18(m,5H),6.02(d,J＝9.4Hz,1H),5.75–5.62(m,1H),5.52(ddt,J＝15.5,8.3,1.4Hz,1H),4.62(q,J＝11.2Hz,2H),4.46(s,2H),4.00(dd,J＝17.1,3.8Hz,2H),3.86(dd,J＝17.1,1.1Hz,2H),3.64(t,J＝8.8Hz,1H),3.45(t,J＝6.5Hz,2H),3.03(s,3H),2.11–1.99(m,2H),1.57(t,J＝6.8Hz,2H),1.43–1.29(m,4H).
13 C NMR(101MHz,CD 3 CN)δ168.6,168.6,140.2,133.9,129.3,128.6,128.4,128.3,94.8,78.9,73.2,71.0,63.8,63.7,47.0,33.1,30.3,29.8,26.6.
11 B NMR(128MHz,CD 3 CN)δ10.6.
ESI-MS:calculated C 22 H 30 BCl 3 N 2 O 8 S[M+Na] + ,621.0776；Found 621.0776.
EXAMPLE 40 Synthesis of Compound 5ca
(E) -2- (1-cyclopropylex-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 65 percent.
Compound 5ca is:
2,2-trichloroethyl (E) - (1-cyclopropyl-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hex-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ca was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ5.81(dt,J＝14.6,6.8Hz,1H),5.66(s,1H),5.56(d,J＝15.8Hz,1H),4.80–4.66(m,2H),3.99(d,J＝16.4Hz,2H),3.83(dd,J＝47.0,17.0Hz,2H),3.12(s,3H),2.04(q,J＝7.2Hz,3H),1.43–1.31(m,3H),0.89(t,J＝7.4Hz,4H),0.59–0.52(m,2H),0.52–0.41(m,2H).
13 C NMR(126MHz,CD 3 CN)δ168.8,168.4,133.4,128.1,94.9,78.7,64.3,64.0,47.5,35.7,23.3,16.1,14.0,2.9,2.1.
11 B NMR(160MHz,CD 3 CN)δ10.34.
ESI-MS:calculated C 16 H 24 BCl 3 N 2 O 7 S[M+Na] + ,527.0355；Found 527.0360.
EXAMPLE 41 Synthesis of Compound 5cb
(E) -6-methyl-2- (pent-3-en-2-yl) -1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 69 percent.
Compound 5cb is:
2,2-trichloroethyl (E) - (2- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) pent-3-en-2-yl) sulfofamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5cb was performed with the following results:
1 H NMR(500MHz,)δ5.91(d,J＝15.8Hz,1H),5.83(s,1H),5.57–5.42(m,1H),4.67(d,J＝1.7Hz,2H),3.99(dd,J＝17.0,8.6Hz,2H),3.79(dd,J＝74.6,17.1Hz,2H),3.08(s,3H),1.69(d,J＝6.3Hz,3H),1.52(s,3H).
13 C NMR(126MHz,None)δ169.0,168.1,133.7,126.3,94.8,78.7,64.3,64.0,47.4,22.1,18.4.
11 B NMR(128MHz,CD 3 CN)δ10.17.
ESI-MS:calculated C 12 H 18 BCl 3 N 2 O 7 S[M+Na] + ,472.9886；Found 472.9887.
EXAMPLE 42 Synthesis of Compound 5cc
(E) -6-methyl-2- (oct-2-en-4-yl) -1,3,6,2-dioxazaborocane-4,8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 76%.
Compound 5cc is:
2,2-trichloroethyl (E) - (4- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) oct-2-en-4-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5cc resulted in the following:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.03(d,J＝16.0Hz,1H),5.77(s,1H),5.47(dq,J＝16.0,6.4Hz,1H),4.69(s,2H),3.94(dd,J＝17.0,5.5Hz,2H),3.82(d,J＝17.4Hz,1H),3.63(d,J＝16.6Hz,1H),3.09(s,3H),1.92–1.78(m,2H),1.68(d,J＝6.5Hz,3H),1.51–1.39(m,2H),1.35–1.28(m,2H),0.93(t,J＝7.3Hz,3H).
13 C NMR(101MHz,CD 3 CN)δ169.3,168.0,133.7,126.2,94.9,78.6,64.1,63.9,47.3,37.8,27.2,24.1,18.7,14.5.
11 B NMR(128MHz,CD 3 CN)δ10.05.
ESI-MS:calculated C 15 H 24 BCl 3 N 2 O 7 S[M+Na] + ,515.0355；Found 515.0353.
EXAMPLE 43 Synthesis of Compound 5cd
(E) -6-methyl-2- (oct-4-en-3-yl) -1,3,6,2-dioxazaborocane-4,8-dione was sequentially added to the reaction tube (0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid with the yield of 84 percent.
Compound 5cd is:
2,2-trichloroethyl (E) - (3- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) oct-4-en-3-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of Compound 5cd was performed, with the following results:
1 h NMR (500 MHz, acetonitrile-d) 3 )δ6.02(dt,J＝16.0,1.5Hz,1H),5.80(s,1H),5.47(dt,J＝16.0,6.8Hz,1H),4.72–4.67(m,2H),3.94(dd,J＝17.0,10.6Hz,2H),3.87–3.61(m,2H),3.10(s,3H),2.05–1.87(m,5H),1.40–1.28(m,2H),1.01(t,J＝7.5Hz,3H),0.88(t,J＝7.4Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ169.3,168.0,132.5,131.7,94.9,78.6,64.0,64.0,47.4,35.9,30.5,23.1,14.1,9.4.
11 B NMR(160MHz,CD 3 CN)δ10.24.
ESI-MS:calculated C 15 H 24 BCl 3 N 2 O 7 S[M+Na] + ,515.0355；Found 515.0353.
EXAMPLE 44 Synthesis of Compound 5ce
Sequentially adding (E) -2- (1-cyclohexyl-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 78%.
Compound 5ce is:
2,2-trichloroethyl (E) - (1-cyclohexyl-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) hex-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of Compound 5ce was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d 3 )δ6.02(dt,J＝16.3,1.5Hz,1H),5.57(s,1H),5.43(dt,J＝16.3,6.8Hz,1H),4.79–4.66(m,2H),3.91(dd,J＝17.0,5.5Hz,2H),3.87–3.58(m,2H),3.12(s,3H),2.06–1.99(m,2H),1.93–1.71(m,4H),1.66–1.59(m,1H),1.43–1.11(m,8H),0.89(t,J＝7.3Hz,3H).
13 C NMR(101MHz,CD 3 CN)δ169.2,168.3,130.9,129.9,94.9,78.6,64.2,64.0,47.8,46.5,36.0,29.3,28.4,27.9,27.7,27.4,23.1,14.1.
11 B NMR(128MHz,CD 3 CN)δ10.10.
ESI-MS:calculated C 19 H 30 BCl 3 N 2 O 7 S[M+Na] + ,569.0825；Found 569.0820.
EXAMPLE 45 Synthesis of Compound 5cf
Sequentially adding (E) -6-methyl-2- (1-phenacylhept-3-en-2-yl) -1,3,6, 2-dioxazaborolane-4, 8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 81 percent.
Compound 5 cf:
2,2-trichloroethyl (E) - (2- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) -1-phenacylhept-3-en-2-yl) sulfoamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 5cf was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ7.42–7.32(m,2H),7.32–7.17(m,3H),6.08(dt,J＝16.0,1.6Hz,1H),5.61(dt,J＝16.0,6.8Hz,1H),5.34(s,1H),4.83–4.67(m,2H),4.01–3.86(m,2H),3.73(dd,J＝38.1,17.1Hz,2H),3.33–3.13(m,2H),3.11(s,3H),2.05(q,J＝7.1,Hz,2H),1.40–1.34(m,2H),0.89(t,J＝7.3Hz,3H).
13 C NMR(101MHz,CD 3 CN)δ169.2,168.1,138.2,132.5,132.5,131.4,128.5,127.3,94.8,78.7,64.3,64.2,47.5,43.2,36.0,23.1,14.1.
11 B NMR(160MHz,CD 3 CN)δ10.07.
ESI-MS:calculated C 20 H 26 BCl 3 N 2 O 7 S[M+Na] + ,577.0512；Found 577.0520.
EXAMPLE 46 Synthesis of Compound 5cg
Sequentially adding (E) -2- (1-cyclopentyl-2-en-1-yl) -6-methyl-1,3,6, 2-dioxazaborolane-4, 8-dione into a reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is light yellow solid, and the yield is 78%.
Compound 5cg was:
2,2-trichloroethyl (E) - (1-cyclen-1- (6-methyl-4, 8-diox-1, 3,6, 2-dioxaborolan-2-yl) but-2-en-1-yl) sulfamate, having the structure shown below:
nuclear magnetic resonance and high resolution characterization of Compound 5cg was performed with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ6.08(dd,J＝16.0,1.9Hz,1H),5.65(s,1H),5.51(dq,J＝16.0,6.4Hz,1H),4.79–4.66(m,2H),3.93(dd,J＝17.0,2.8Hz,2H),3.72(dd,J＝80.3,17.0Hz,3H),3.12(s,3H),2.48(ddd,J＝17.3,10.0,7.2Hz,1H),1.68(dd,J＝6.5,1.6Hz,7H),1.59–1.39(m,5H).
13 C NMR(101MHz,CD 3 CN)δ169.3,168.1,131.2,126.3,94.9,78.6,64.3,64.1,47.7,28.4,27.9,25.5,25.1,18.9.
11 B NMR(128MHz,CD 3 CN)δ10.0.
ESI-MS:calculated C 16 H 24 BCl 3 N 2 O 7 S[M+Na] + ,527.0355；Found 527.0353.
EXAMPLE 47 Synthesis of Compound 5ch
(E) -6-methyl-2- (6-methylhept-2-en-4-yl) -1,3,6, 2-dioxaborolane-4, 8-dione was added to the reaction tube in this order(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 73 percent.
Compound 5ch is:
2,2-trichloroethyl (E) - (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborocan-2-yl) hept-2-en-4-yl) sulfamate, having the structure shown below:
/>
nuclear magnetic resonance and high resolution characterization of compound 5ch was performed as follows:
1 h NMR (500 MHz, acetonitrile-d) 3 )δ6.03(dd,J＝16.0,1.7Hz,1H),5.83(s,1H),5.47(dq,J＝15.9,6.5Hz,1H),4.75–4.65(m,2H),3.94(dd,J＝17.1,2.1Hz,2H),3.72(dd,J＝103.7,17.0Hz,2H),3.11(s,3H),2.04–1.96(m,1H),1.88–1.73(m,2H),1.67(dd,J＝6.4,1.7Hz,3H),1.00(d,J＝6.6Hz,3H),0.96(d,J＝6.6Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ169.4,168.1,133.6,126.4,94.9,78.6,64.2,64.0,47.4,46.3,25.6,25.0,24.7,18.8.
11 B NMR(128MHz,CD 3 CN)δ10.1.
ESI-MS:calculated C 15 H 24 BCl 3 N 2 O 7 S[M+Na] + ,515.0355；Found 515.0360.
EXAMPLE 48 Synthesis of Compound 5da
2- ((E) -hex-2-en-1-yl) -6- ((1R, 2R,3R, 5S) -2, 6-trimethylyclo [ 3.1.1) was added sequentially to the reaction tube]heptan-3-yl)-1,3,6,2-dioxazaborocane-4,8-dione(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 68 percent.
Compound 5da is:
2,2-trichloroethyl ((E) -1- (4, 8-dioxo-6- ((1R, 2R,3R, 5S) -2, 6-trimethyliceclo [3.1.1] heptan-3-yl) -1,3,6, 2-dioxazaborocan-2-yl) hex-2-en-1-yl) sulfofamate having the structure shown below:
nuclear magnetic resonance and high resolution characterization of Compound 5da was performed as follows:
1 H NMR (500 MHz, acetonitrile-d) 3 )δ6.25(d,J＝10.5Hz,1H),5.77–5.66(m,1H),5.54(ddt,J＝15.5,8.3,1.5Hz,1H),4.73–4.58(m,3H),4.24–4.18(m,2H),,3.98(d,J＝2.6Hz,2H),3.81(d,J＝18.0Hz,1H),3.78–3.72(m,1H),2.76–2.66(m,1H),2.41(ddd,J＝11.4,6.0,2.1Hz,1H),2.28(d,J＝2.4Hz,1H),2.10–2.02(m,2H),2.00(ddd,J＝8.9,5.6,2.2Hz,1H),1.90(td,J＝6.0,2.4Hz,1H),1.61(ddd,J＝14.8,5.8,2.8Hz,1H),1.44–1.38(m,2H),1.28(d,J＝6.9Hz,3H),1.24(s,3H),1.01(s,3H),0.91(t,J＝7.4Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ169.7,167.2,133.2,128.0,94.3,78.7,67.8,62.1,56.3,49.5,41.3,39.3,38.8,34.8,31.5,30.7,27.1,23.2,23.1,22.7,13.6.
11 B NMR(160MHz,CD 3 CN)δ10.7.
ESI-MS:calculated C 22 H 34 BCl 3 N 2 O 7 S[M+Na] + ,609.1138；Found 609.1143.
EXAMPLE 49 Synthesis of Compound 5ea
(E) -2- (hex-2-en-1-yl) -5,5,6,7,7-pentamethyl-1,3,6, 2-dioxazaborolane-4, 8-dione was sequentially added to the reaction tube(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is obtained by silica gel column chromatography purification, and is white solid with the yield of 68 percent.
Compound 5ea is:
2,2-trichloroethyl (E) - (1- (5,5,6,7,7-pentamethyl-4, 8-diox-1, 3,6, 2-dioxazaborocan-2-yl) hex-2-en-1-yl) sulfofamate, the structure of which is shown below:
nuclear magnetic resonance and high resolution characterization of compound 5ea was performed as follows:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ5.95(d,J＝9.5Hz,1H),5.66(dt,J＝15.5,6.6Hz,1H),5.57–5.49(m,1H),4.66–4.56(m,2H),3.65(t,J＝8.9Hz,1H),2.71(s,3H),2.02(q,J＝6.8Hz,2H),1.66(d,J＝16.8Hz,6H),1.59(d,J＝14.4Hz,6H),1.40(qd,J＝7.4,3.7Hz,2H),0.91(t,J＝7.3Hz,3H).
13 C NMR(126MHz,CD 3 CN)δ174.6,174.6,132.8,128.9,94.4,78.4,37.2,34.8,30.5,22.7,13.6.
11 B NMR(128MHz,CD 3 CN)δ8.0.
ESI-MS:calculated C 17 H 28 BCl 3 N 2 O 7 S[M+Na] + ,543.0668；Found 543.066.
EXAMPLE 50 Synthesis of Compound 6a
2- (Cyclohex-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the reaction tube in sequence(0.2 mmol,1.0 equiv.) trichloroethyl sulfonic acid amine (0.4 mmol,2.0 equiv.) selenium catalyst (0.05 mmol,0.25 equiv.) iodobenzene diacetic acid (1.0 mmol,5.0 equiv.) 2.0mL dichloromethane solvent. The reaction tube was sealed, argon was introduced, and the reaction mixture was stirred at 35℃to effect a reaction. After the reaction is finished, the reaction solution is diluted by ethyl acetate, the solvent is dried in vacuum, and the product is purified by silica gel column chromatography, and is white solid with the yield of 73 percent.
Compound 6a is:
2,2-trichloroethyl (1- (6-methyl-4, 8-dioxo-1,3,6, 2-dioxazaborolan-2-yl) cyclohex-2-en-1-yl) sulfoamate having the structure shown below:
nuclear magnetic resonance and high resolution characterization of compound 6a was performed, with the following results:
1 h NMR (400 MHz, acetonitrile-d) 3 )δ5.98(dt,J＝10.2,3.6Hz,2H),5.90(dt,J＝10.3,2.0Hz,1H),5.74(s,1H),4.68(d,J＝1.7Hz,2H),4.00(dd,J＝17.0,5.7Hz,2H),3.88(dd,J＝17.1,8.7Hz,2H),3.11(s,3H),2.12–2.02(m,2H),1.93–1.85(m,2H),1.83–1.74(m,2H).
13 C NMR(126MHz,None)δ168.9,168.1,133.1,126.4,94.9,78.8,64.5,63.8,47.6,32.4,25.0,18.9.
11 B NMR(128MHz,CD 3 CN)δ10.16.
ESI-MS:calculated C 13 H 18 BCl 3 N 2 O 7 S[M+Na] + 484.9886; found 484.9879 comparative example 1
This comparative example is reported in the literature using a catalyst [ Cp IrCl ] 2 ] 2 、AgBF 4 Catalytic reactionWith p-toluenesulfonyl azide TsN 3 The reaction of (2) comprises the following specific steps:
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the pressure-resistant tube in this order(0.2mmol，1.0equiv)，TsN 3 (0.4mmol，2.0equiv)，[Cp*IrCl 2 ] 2 (0.03mmol，15mol％)，AgBF 4 (0.12 mmol,60 mol%), liOAc (0.2 mmol,1.0 equiv). 1.0mL of ethyl acetate solvent was added to the glove box, and the mixture was stirred for 1 minute, and the pressure-resistant pipe was sealed with a screw plug, and the reaction mixture was stirred at 35℃to react. The reaction was monitored after 12 hours and the results showed that no reaction occurred.
Comparative example 2
This comparative example is reported in the literature using a catalyst [ Cp IrCl ] 2 ] 2 、AgBF 4 Catalytic reactionAnd->The reaction of (2) comprises the following specific steps:
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the pressure-resistant tube in this order(0.2mmol，1.0equiv)，/>(0.4mmol，2.0equiv)，[Cp*IrCl 2 ] 2 (0.03mmol，15mol％)，AgBF 4 (0.12 mmol,60 mol%), liOAc (0.2 mmol,1.0 equiv). 1.0mL of ethyl acetate solvent was added to the glove box, and the mixture was stirred for 1 minute, and the pressure-resistant pipe was sealed with a screw plug, and the reaction mixture was stirred at 40℃to react. The reaction was monitored after 12 hours and the results showed that no reaction occurred.
Comparative example 3
This comparative example is reported in the literature using a catalyst [ Cp IrCl ] 2 ] 2 、AgSbF 6 Catalytic reactionWith p-toluenesulfonamide TsNH 2 The reaction of (2) comprises the following specific steps:
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the pressure-resistant tube in this order(0.2mmol，1.0equiv)，TsNH 2 (0.4mmol，2.0equiv)，[Cp*IrCl 2 ] 2 (0.004mmol，2mol％)，AgSbF 6 (0.02 mmol,10 mol%) AgOAc (0.44 mmol,2.2 equiv). 1.0mL of ethyl acetate solvent was added to the glove box, and the mixture was stirred for 1 minute, and the pressure-resistant pipe was sealed with a screw plug, and the reaction mixture was stirred at 60℃to react. The reaction was monitored after 12 hours and the results showed that no reaction occurred.
Comparative example 4
This comparative example is reported in the literature to be catalyzed by the catalyst AgOTfWith p-toluenesulfonamide TsNH 2 The reaction of (2) comprises the following specific steps:
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the pressure-resistant tube in this order(0.2mmol，1.0equiv)，TsNH 2 (0.4 mmol,2.0 equiv), agOTf (0.02 mmol,10 mol%), tripyridine TPY (0.024 mmol,12 mol%), iodinated benzene PhIO (0.24 mmol,1.2 equiv). 1.0mL of ethyl acetate solvent was added to the glove box, and the mixture was stirred for 1 minute, and the pressure-resistant pipe was sealed with a screw plug, and the reaction mixture was stirred at room temperature to react. The reaction was monitored after 12 hours and the results showed that no reaction occurred.
Comparative example 5
This comparative example is reported in the literature using a catalyst [ RhCp (MeCN) 3 ]、AgSbF 6 Catalytic reactionAnd->The reaction of (2) comprises the following specific steps:
(E) -2- (hept-2-en-1-yl) -6-methyl-1,3,6,2-dioxazaborocane-4,8-dione was added to the pressure-resistant tube in this order(0.2mmol，1.0equiv)，/>(0.4mmol，2.0equiv)，[RhCp*(MeCN) 3 ](0.01mmol，5mol％)，AgSbF 6 (0.06 mmol,30 mol%) CsOAc (0.01 mmol,5 mol%). 1.0mL of ethyl acetate solvent was added to the glove box, and the mixture was stirred for 1 minute, and the pressure-resistant pipe was sealed with a screw plug, and the reaction mixture was stirred at 40℃to react. The reaction was monitored after 12 hours and the results showed that no reaction occurred.
Comparative example 6
The main difference between this comparative example and example 1 is that: replacement of the oxidant iodobenzene diacetic acid with hydrogen peroxide, mCPBA (meta-chloroperoxybenzoic acid), DMP (dimethyl phthalate), PCC (pyridinium chlorochromate), KMnO 4 Or TBHP (t-butyl hydroperoxide), which showed no reaction.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (5)

1. A preparation method of an alpha-amino boron-based compound is characterized by comprising the following steps: the method comprises the following steps: under the existence of selenium catalyst and high-valence iodine oxidant, making allylboron compound and sulfonamide or amine sulfonate react to obtain alpha-aminoboron compound;
the selenium catalyst is IMeSe;
the high-valence iodine oxidant is iodobenzene diacetic acid;
the structural formula of the allylboron compound is shown as a formula (1), the structural formula of the sulfonamide is shown as a formula (2), and the structural formula of the sulfonic acid amine is shown as a formula (3); the structural formula of the alpha-amino boron-based compound is shown as a formula (4) or (5);
wherein R is 1 Is C 1 ～C 10 C is a hydrocarbon group of (C) 1 ～C 10 Substituted hydrocarbyl, halogen, phenyl, substituted phenyl, heterocyclic aromatic, substituted heterocyclic aromatic, cyano, ester, ether, benzyloxy, substituted benzyloxy, siloxane or dioxan;
R 2 h, C of a shape of H, C 1 ～C 6 A hydrocarbyl group, a phenyl group, or a substituted phenyl group;
R 3 is H or C 1 ～C 6 Is a hydrocarbon group of (2);
R 4 is C 1 ～C 10 Is a hydrocarbon group of (2);
R 5 is methyl, phenyl, trifluoromethyl, p-bromophenyl, p-fluorophenyl, p-tolyl, p-chlorophenyl, 4-t-butylphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl or o-nitrophenyl A base;
R 6 is trifluoromethyl, trifluoroethyl, trichloroethyl, phenyl, p-methoxyphenyl, 4-methyl phenyl, hexafluoroisopropyl or trifluoroethyl;
the C is 1 ～C 10 Substituted hydrocarbyl of (2) is selected from halogen, cyano, phenyl, hydroxy, amino, sulfonic acid, p-benzenesulfonic acid, azide, benzyloxy, substituted benzyloxy, siloxane, and siloxy substituted C 1 ～C 10 Fatty alkyl, C 1 ～C 10 Naphthene radical, C 1 ～C 10 Aliphatic alkylene or C 1 ～C 10 Aliphatic alkyne groups;
the substituted phenyl is selected from C 1 ～C 6 Alkanes, halogens, nitro, cyano, hydroxy, sulfonic acid groups, C 1 ～C 6 Phenyl substituted by one or more groups in alkoxy;
the heterocyclic aromatic hydrocarbon group is selected from C 5 ～C 20 A heterocyclic aromatic hydrocarbon group containing any one of N, S, O elements;
the substituent in the heterocyclic aromatic hydrocarbon group containing the substituent is selected from C 1 ～C 6 One or more of alkane, halogen, cyano, phenyl, hydroxy, sulfonic acid, p-benzenesulfonic acid, azide, carbonyl;
the ester group is selected from the group consisting of-R 1a -COO-R 1b Or R is 1a -COO-R 1b -, wherein R is 1a 、R 1b Are independently selected from C 1 ～C 14 A hydrocarbyl group, a phenyl group, or a substituted phenyl group;
the ether group is selected from the group consisting of-R 1c -O-R 1d Wherein R is 1c 、R 1d Are independently selected from C 1 ～C 14 A hydrocarbyl group, a phenyl group, or a substituted phenyl group;
the substituted benzyloxy group is selected from the group consisting of C on the benzene ring 1 ～C 6 Benzyloxy of one or more substituents selected from alkane, halogen, cyano, phenyl, hydroxy, sulfonic acid, p-benzenesulfonic acid, azide, and carbonyl;
the siloxane groups are selected from the group consisting of-OSiR 1e R 1f R 1g Wherein R is 1e 、R 1f 、R 1g Are independently selected from C 1 ～C 14 A hydrocarbyl group, a phenyl group, or a substituted phenyl group.
2. The method of manufacture of claim 1, wherein: the C is 1 ～C 10 Is selected from C 1 ～C 10 Fatty alkyl, C 1 ～C 10 Naphthene radical, C 1 ～C 10 Aliphatic alkylene group, C 1 ～C 10 One of the fatty alkyne groups.
3. The method of manufacture of claim 1, wherein: the heterocyclic aromatic hydrocarbon group is selected from furyl, pyrrolyl, thienyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, benzofuranyl, indolyl, triazolyl, benzotriazolyl or phthalimidyl.
4. The method of manufacture of claim 1, wherein: the molar ratio of the allyl boron compound to the high-valence iodine oxidizer to the selenium catalyst is 1:1 to 6:0.1 to 0.5.
5. The method of manufacture of claim 1, wherein: the molar ratio of the allyl boron compound to the sulfonamide or the sulfonic acid amine is 1:1 to 3.
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