CN114634407B - Method for stereospecifically synthesizing 2-enal, 2-enone compound and deuterated compound thereof - Google Patents

Method for stereospecifically synthesizing 2-enal, 2-enone compound and deuterated compound thereof Download PDF

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CN114634407B
CN114634407B CN202011485720.3A CN202011485720A CN114634407B CN 114634407 B CN114634407 B CN 114634407B CN 202011485720 A CN202011485720 A CN 202011485720A CN 114634407 B CN114634407 B CN 114634407B
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mmol
rhodium
nmr
cdcl
petroleum ether
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CN114634407A (en
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麻生明
王维一
于一博
钱辉
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Fudan University
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing 2-enal and 2-enone compound and deuterated compound thereof in stereospecific mode, namely 2, 3-dienol and organic boric acid react in an organic solvent under the action of rhodium catalyst, copper catalyst, alkali and air (or oxygen), and the 2-enal and 2-enone compound and deuterated compound thereof are synthesized in one step in stereospecific mode. The method has the advantages of simple operation, easily obtained raw materials and reagents, mild reaction conditions, wide substrate universality, good functional group compatibility and stereospecificity (single configuration) of the reaction. The method can be used for synthesizing deuterated 2-enal and deuterated 2-enone and structurally modifying drug molecules and natural product molecules.

Description

Method for stereospecifically synthesizing 2-enal, 2-enone compound and deuterated compound thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for stereospecifically synthesizing 2-enal, 2-enone compounds and deuterated compounds thereof.
Background
2-enal and 2-enone compounds are very important compounds in organic chemistry, have conjugated structures, thus have various chemical properties, are very important and widely applied synthetic building blocks widely used in the fields of organic synthesis, pharmaceutical chemistry, material chemistry and the like, and can participate in various transformations (Ref (a) Klier, L.; tur, F.; poulsen, P.H.; K.a. chem.soc.rev.2017,46,1080-1102. (b) Afewerki, s.; c.rdova, a.chem.rev.2016,116,13512-13570 (C) Marcos, v.; alem an, j.chem.soc.rev.2016,45,6812-6832 (d) Li, j. -l; liu, t. -y; chen, y. -c.acc.chem.res.2012,45,1491-1500 (e) ends, d.; grondal, c.; huttl, M.R.M.Angew.chem.int.ed.2007,46, 1570-1581.). Stereoselective synthesis of 2-enal and 2-enone compounds has been extremely challenging (Ref (a) Milstein, d.; stille, j.k.j.org.chem.1979,44,1613.; eddarir, s.; cotele, n.; bakkur, y.; rolado, c.tetrahedron lett.2003,44,5359.; thiot, c.; mioskowski, c.; wagner, a.eur.j.org.chem.2009, 3219.; biancog. Canarschia, c.; farina, a.; gso, m.; mar, c.tetrahedron lett.2003,44,9107.; finan, p.dra.; fogg.62. Chem.62. J.62. Chem., j.62. 6. Fig. j.m.; m.62. 6. Fig. 62, j.30.). For 3, 3-disubstituted 2-enals and 2-enone, controlling the steric configuration of the double bond is the biggest difficulty. Therefore, the development of a stereospecific synthesis method of polysubstituted 2-enal and 2-enone compounds has important theoretical significance and wide application value, and is a great breakthrough to the existing synthesis method.
The later modification of complex molecules such as drugs and natural products is a highly efficient synthetic strategy, which is a powerful means for promoting the development of new drugs and drug research (Ref: cernak, t.; dykstra, k.d.; tyagajan, s.; vacal, p.; krska, s.w.chem.soc.rev.2016,45, 546-576.). The α, β -unsaturated ketone fragments are an important class of covalent inhibitors "warheads" (Ref (a) Liu, q.; sabnis, y.; zhao, z.; zhang, t.; buhrlage, s.j.; jones, l.h.; gray, n.s.chem.biol.2013,20, 146-159.; zhao, z.; bourne, p.e. drug discovery.today 2018,23, 727-735.). Therefore, the 2-ketene fragment obtained by direct post-modification from complex molecules can provide a powerful tool for the research of covalent inhibitors and even the research of medicines, and has important significance.
Deuterated compounds are widely used in pharmaceutical research (Ref: pirali, t.; serafini, m.; cargnin, s.; genazzani, a.a. j. Med. Chem.2019,62, 5276-5297.), in mechanism research (Ref: G mez-gallgo, m.; sierra, m.a. chem. Rev.2011,111, 4857-4963.); biochemical research (Ref: atzrodt, j.; derdau, v.; kerr, w.j.; reid, m.angelew.chem.int. Ed.2018,57, 1758-1784.). Since the first deuterated drug Austedo (Ref: schmidt, c.nat. Biotechnol.2017,35, 493-494.) was approved by the U.S. Food and Drug Administration (FDA), the study of deuterated drugs has been rapidly developed (Ref (a) Atzrodt, j.; derdau, v.; fey, t.; zimmemann, j.angelw.chem. In. Ed.2007,46, 7744-7765.; atzrodt, j.; derdau, v.; kerr, w.j.; reid, m.angelw.chem. Int. Ed.2018,57, 3022-3047.; c) Valero, m.; derdeu, v.j.label. Compd. Radiaha.2019, 1-15), new synthetic methods for deuterated compounds have been urgently required. The existing synthetic method of the deuterated compound is difficult to accurately and flexibly control the number of deuterium atoms on the same carbon atom, and the deuterated synthetic method with specificity of development sites is a great breakthrough to the existing method.
Disclosure of Invention
The invention aims to provide a method for stereospecifically synthesizing 2-enal and/or 2-enone compounds and deuterated compounds thereof. The invention synthesizes 2-enal and/or 2-enone compound and deuterated compound thereof in one step in a stereospecific way through the reaction of 2, 3-dienol and organic boric acid in an organic solvent under the action of rhodium catalyst, copper catalyst, alkali and air (or oxygen). The method has the advantages of simple operation, easily obtained raw materials and reagents, mild reaction conditions, wide substrate universality, good functional group compatibility, stereospecificity (single configuration) of the reaction, and high research significance and practical value. The method can be used for synthesizing deuterated 2-enal and deuterated 2-enone and structurally modifying drug molecules and natural product molecules.
The invention provides a method for synthesizing 2-enal and/or 2-enone compound and deuterated compound thereof in stereospecific mode, namely 2, 3-dienol reacts with organic boric acid in a first organic solvent under the action of rhodium catalyst, copper catalyst, alkali and air (or oxygen), and the 2-enal and/or 2-enone compound and deuterated compound thereof are synthesized in one step in stereospecific mode; the reaction process is shown in the following reaction formula (a):
The reaction formula (a);
in the reaction scheme (a),
R 1 is phenyl, aryl, heterocyclic, hydrocarbon with functional group;
R 2 hydrogen, isotopes of hydrogen (deuterium, tritium), phenyl, aryl, heterocyclyl, hydrocarbyl with functional groups;
R 3 hydrogen, isotopes of hydrogen (deuterium, tritium), phenyl, aryl, heterocyclyl, hydrocarbyl with functional groups;
H a hydrogen, isotopes of hydrogen (deuterium, tritium);
H b is hydrogen, an isotope of hydrogen (deuterium,Tritium);
wherein the R is 1 、R 2 、R 3 Wherein the aryl is phenyl with substituent groups at the ortho, meta and para positions, and the substituent groups comprise alkyl, alkenyl, phenyl, halogen, trifluoromethyl, alkoxy, alkoxycarbonyl, acyl, acyloxy, amido, sulfonyl, sulfonyloxy, hydroxyl, nitro, carboxyl, cyano and amino; the R is 1 、R 2 、R 3 The heterocyclic group in (a) refers to a 3-10 membered heterocyclic ring with a ring-forming atom being carbon, nitrogen, oxygen or sulfur, and the heterocyclic ring is an aliphatic ring, an aromatic ring or a ring formed by splicing two or more simple rings; the R is 1 、R 2 、R 3 The functional group in the C1-C40 hydrocarbon group with functional group in (2) includes acyl, hydroxyl, halogen, alkoxy, alkoxycarbonyl, formyl, acyloxy, amido, sulfonyl, sulfonyloxy, nitro, carboxyl and cyano.
Preferably, the method comprises the steps of,
R 1 phenyl, aryl, heterocyclic, C1-C40 alkyl with functional group;
R 2 hydrogen, isotopes of hydrogen (deuterium, tritium), phenyl, aryl, heterocyclyl, C1-C40 hydrocarbyl bearing functional groups;
R 3 hydrogen, isotopes of hydrogen (deuterium, tritium), phenyl, aryl, heterocyclyl, C1-C40 hydrocarbyl bearing functional groups;
H a hydrogen, isotopes of hydrogen (deuterium, tritium);
H b hydrogen, isotopes of hydrogen (deuterium, tritium);
wherein the R is 1 、R 2 、R 3 Wherein the aryl is phenyl with substituent groups at the ortho, meta and para positions, and the substituent groups comprise C1-C40 alkyl, C2-C40 alkenyl, phenyl, halogen, trifluoromethyl, C1-C40 alkoxy, C1-C40 alkoxycarbonyl, acyl, acyloxy, amido, sulfonyl, sulfonyloxy, hydroxyl, nitro, carboxyl, cyano and amino; the R is 1 、R 2 、R 3 The heterocyclic group in (a) refers to a 3-10 membered heterocyclic ring with a ring-forming atom being a carbon, nitrogen, oxygen or sulfur atom, and is an aliphatic ring or an aromatic ringOr a ring formed by splicing two or more simple rings, including thiophene, furan, pyrrole, pyridine; the R is 1 、R 2 、R 3 The functional group in the C1-C40 hydrocarbon group with functional group in (2) includes acyl, hydroxyl, halogen, C1-C40 alkoxy, C1-C40 alkoxycarbonyl, formyl, acyloxy, amido, sulfonyl, sulfonyloxy, nitro, carboxyl and cyano.
It is further preferred that the composition comprises,
R 1 phenyl, 4-methylphenyl, 3-methoxyphenyl, 4-bromophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 4-acetylphenyl, 4-methoxycarbonylphenyl, 3-cyanophenyl, 3-nitrophenyl, 4-biphenyl, 2-naphthyl, 3-furyl, 2-thienyl, 3-thienyl, 4-formyl, 4-cyano, 1-pentenyl, cyclopropyl, methyl;
R 2 is hydrogen, deuterium, phenyl, 2-methylphenyl, 3-methylphenyl, 4-bromophenyl, 1-naphthyl, cyclohexyl, n-hexyl, 2, 6-dimethyl-5-heptenyl, n-pentyl;
R 3 hydrogen, deuterium, phenyl, 4-methylphenyl, 3-thienyl, 4-trifluoromethylphenyl, n-propyl;
H a hydrogen, deuterium;
H b is hydrogen, deuterium.
The method for synthesizing the 2-enal and/or 2-ketene compound and the deuterated compound thereof by stereospecificity comprises the following steps:
(1) Sequentially adding a rhodium catalyst, alkali, a copper catalyst, organic boric acid, 2, 3-dienol and a first organic solvent into a dried reaction tube, plugging the reaction tube with a rubber plug, inserting an air ball (or an oxygen ball) to make the reaction tube in an air (or oxygen) atmosphere, and stirring and reacting at-20-60 ℃;
Wherein the first organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane, toluene, acetonitrile, methanol, ethanol, dichloromethane, diethyl ether, anisole, methyl tertiary butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and the like; preferably tetrahydrofuran.
Wherein the dosage of the first organic solvent is 1.0-20.0mL/mmol based on the dosage of the 2, 3-dienol shown in the reaction formula (a); preferably 5.0-10.0mL/mmol.
(2) After the reaction in the step (1) is completed, filtering the mixed solution in the reaction tube by using a short column of silica gel, washing the mixed solution by using a second organic solvent, concentrating the mixed solution, and performing rapid column chromatography to obtain the corresponding 2-enal or 2-enone compound and deuterated compound thereof;
wherein the second organic solvent is one or more of ethyl acetate, diethyl ether, methanol, ethanol, dichloromethane, tetrahydrofuran, 1, 4-dioxane, acetone, acetonitrile and the like; preferably, ethyl acetate.
Wherein the second organic solvent is 1.0-200mL/mmol based on the amount of 2, 3-dienol shown in the reaction formula (a); preferably 20-100mL/mmol.
The method for synthesizing the 2-enal and the 2-enone compounds and the deuterated compounds thereof in a stereospecific way comprises the following steps:
wherein the first organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane, toluene, acetonitrile, methanol, ethanol, dichloromethane, diethyl ether, anisole, methyl tertiary butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and the like; preferably tetrahydrofuran.
Wherein the rhodium catalyst is any one or more of dichloro (pentamethyl cyclopentadienyl) rhodium (III) dimer, tris (triphenylphosphine) rhodium (I) chloride, bis (ethylene) rhodium (I) chloride dimer, (1, 5-cyclooctadiene) rhodium (I) chloride dimer, bis (ethylene) acetylacetonate rhodium (I), (1, 5-cyclooctadiene) rhodium (I) chloride dimer, bis (norbornadiene) rhodium tetrafluoroborate (I), rhodium (II) acetate dimer, bis (hexafluoroantimonic acid) triacetonitrile (pentamethyl cyclopentadienyl) rhodium (III), acetylacetonate rhodium (III), pentachlororhodium (III) dichloride, tris (ethylenediamine) rhodium (III) trichloride, potassium pentachlororhodium (III) acid, sodium hexachlororhodium (III) chloride, potassium hexachlororhodium (III) trichloride, rhodium (III) bromide (III), rhodium (III) iodide, rhodium (III) sulfate, rhodium (III) nitrate, potassium hexanitrorhodium (III) trichloride and the like; preferably dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer and bis (hexafluoroantimonic acid) triacetonitrile (pentamethylcyclopentadienyl) rhodium (III).
Wherein the copper catalyst is any one or more of copper acetate hydrate, copper acetate, copper sulfate hydrate, copper sulfate, copper nitrate hydrate, copper nitrate, copper chloride hydrate, copper chloride, copper bromide and the like; preferably, the copper acetate is copper acetate hydrate or copper acetate; further preferred is copper acetate monohydrate.
Wherein the alkali is any one or more of sodium acetate, sodium carbonate, sodium bicarbonate, potassium acetate, potassium carbonate, potassium bicarbonate, cesium carbonate, lithium carbonate, magnesium acetate, calcium acetate and the like; preferably sodium acetate.
Wherein the molar ratio of the rhodium catalyst to the copper catalyst to the alkali to the organic boric acid to the 2, 3-dienol is (0.005-0.10): (0.005-1.20): (0-0.60): (1.0-3.0): 1.0; preferably, (0.010-0.025): (0.05-0.10): (0.20-0.30): (1.5-2.0): 1.0.
wherein the temperature of the reaction is-20 to 60 ℃, preferably 20 to 50 ℃.
Wherein the reaction time is determined according to the extent of progress of the reaction, and varies from 4 to 96 hours, or from 5 to 48 hours, i.e., in some embodiments, 5 hours, to achieve the desired reaction result.
The method for synthesizing the 2-enal and the 2-enone compounds and the deuterated compounds thereof by stereospecificity overcomes the technical difficulty of stereoselectivity and obtains the 2-enal and the 2-enone compounds and the deuterated compounds thereof with specific stereo configuration. The reaction generates 1, 4-hydrogen (or isotope of hydrogen) migration, shows site specificity, and overcomes the difficulty of controllable introduction of deuterium atoms in the synthesis of deuterated compounds.
The method for synthesizing the 2-enal and the 2-ketene compound in a stereospecific way can be applied to the synthesis of deuterated 2-enal and deuterated 2-ketene.
The method for synthesizing the 2-enal and the 2-ketene compound by stereospecific can be applied to structural modification of drug molecules and natural product molecules.
In the invention, the reaction mechanism presumed by the method is shown as the following formula (I): rhodium catalyst Cp Rh 2+ Carrying out transfer metallization with organic boric acid to form an intermediate A; then the intermediate A and the 2, 3-dienol 1 undergo an insertion reaction to form an intermediate B, and the intermediate B is treated with alkali AcO - Under the action of (2) removing hydroxyl hydrogen, simultaneously carrying out beta-elimination, and transferring D at the alpha position of hydroxyl to Rh (III) to form an intermediate C; then reducing and eliminating to obtain Cp Rh and a product E-3; finally, cp Rh is oxidized in the Cu/air oxidation system and regenerated into Cp Rh 2+ The catalytic cycle is completed.
The invention uses 2, 3-dienol and easily available organoboron reagent to obtain the 2-enal and/or 2-enone compound and deuterated compound thereof in a stereospecific one-step manner.
The invention also provides a 2-enal and/or 2-enone compound and a deuterated compound thereof, and the structure of the 2-enal and/or 2-enone compound is shown as a formula 3:
wherein R is 1 、R 2 、R 3 、H a 、H b Is defined as in formula (a).
The beneficial effects of the invention include: compared with the prior art, the method solves the problem of stereoselectivity, and can directly obtain a product with a single configuration in a stereospecific way; the reaction mechanism of the method of the invention involves 1,4-H migration, thus also providing a novel method for synthesizing deuterated 2-enal and deuterated 2-enone; the method provides a novel method for post-modification of complex molecules, and can directly derive 2-enal and 2-ketene structural fragments from the complex molecules; the operation is simple; raw materials and reagents are easy to obtain; the reaction condition is mild; the universality of the substrate is wide; the compatibility of the functional groups is good.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples and reaction schemes, but the present invention is not limited to the following examples. Variations and advantages that would occur to one skilled in the art are included in the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims. The procedures, conditions, reagents, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for those specifically mentioned below, and the present invention is not particularly limited. The following examples are presented to aid in the understanding of the invention, but are not intended to limit the scope of the invention.
And (3) injection: the equiv in the following example reaction formula represents equivalent; mol represents mol; mmol represents millimoles; mol% means the molar ratio calculated on the basis of 2, 3-dienol; [ Cp ] RhCl 2 ] 2 Represents dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer; naOAc represents sodium acetate; cu (OAc) 2 ·H 2 O represents copper acetate monohydrate; THF represents tetrahydrofuran; air means that the reaction is carried out in an air atmosphere; airblock indicates that the reaction is carried out in an air atmosphere by inserting an air ball; ar represents that the reaction is carried out in an argon atmosphere; rt represents room temperature; min represents minutes; h represents hours; ee represents the percent enantiomeric excess; etMgBr represents ethylmagnesium bromide; LDA represents lithium diisopropylamide; pd (Pd) 2 (dba) 3 ·CHCl 3 Represents a tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct; PPh (PPh) 3 Represents triphenylphosphine; cs (cells) 2 CO 3 Represents cesium carbonate; DCM represents dichloromethane; tolene represents toluene; meOH represents methanol; dioxane represents 1, 4-dioxane; meCN represents acetonitrile; cuSO 4 ·5H 2 O represents copper sulfate pentahydrate; cu (NO) 3 ) 2 ·3H 2 O represents copper nitrate trihydrate; petroleum ether boiling range is 60-90 ℃; the silica gel is 300-400 mesh silica gel; the nuclear magnetic yield is calculated by 1 H NMR determination, internal standard dibromomethane; deuteration rate is defined by 1 H NMR determination.
Example 1
Reaction formula (1);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (6.4mg，0.01mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 3-methoxyphenylboronic acid (2 a,232.8mg,1.5 mmol), 1a (70.1 mg,1.0 mmol), THF (5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction solution was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL), and the solvent was removed by rotary evaporation. Separation and purification were performed by silica gel column chromatography (eluent: petroleum ether/ethyl acetate=20/1-10/1) to give product E-3aa (134.0 mg, 76%): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝7.6Hz,1H,CHO),7.32(t,J＝8.0Hz,1H,Ar-H),7.13(d,J＝7.6Hz,1H,Ar-H),7.05(s,1H,Ar-H),6.96(dd,J 1 ＝8.4Hz,J 2 ＝2.0Hz,1H,Ar-H),6.38(d,J＝7.6Hz,1H,＝CH),3.83(s,3H,OCH 3 ),2.55(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.2,159.7,157.5,142.0,129.7,127.3,118.6,115.3,111.9,55.3,16.4；IR(neat):v＝2940,2837,2755,1715,1659,1599,1575,1486,1429,1375,1322,1286,1264,1214,1134,1038cm -1 ；MS(70eV,EI)m/z(％):176(M + ,35.13),135(100).
example 2
Reaction formula (2);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), phenylboronic acid (2 b,186.5mg,1.5 mmol), 1a (70.2 mg,1.0 mmol), THF (5 mL) were reacted for 10 hours to give E-3ab (94.1 mg, 64%) (5% volume fraction of three for silica gel)Petroleum ether basification of ethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/dichloromethane=3/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.18(d,J＝7.6Hz,1H,CHO),7.68-7.48(m,2H,Ar-H),7.47-7.28(m,3H,Ar-H),6.39(d,J＝8.0Hz,1H,＝CH),2.57(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.2,157.5,140.5,130.0,128.7,127.2,126.2,16.3；IR(neat):v＝3058,2855,2759,1715,1655,1620,1574,1493,1443,1376,1325,1246,1141cm -1 ；MS(70eV,EI)m/z(％):146(M + ,44.91),145(100).
example 3
Reaction formula (3);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (6.3mg，0.01mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 4-methylphenylboronic acid (2 c,212.3mg,1.5 mmol), 1a (70.1 mg,1.0 mmol), THF (5 mL), reacted for 5.1 hours to give E-3ac (129.4 mg, 81%) (silica gel was basified with petroleum ether containing 5% volume fraction of triethylamine) (eluent: petroleum ether (containing 0.2% volume fraction of triethylamine)/ethyl acetate=15/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.16(d,J＝7.6Hz,1H,CHO),7.45(d,J＝8.0Hz,2H,Ar-H),7.21(d,J＝8.0Hz,2H,Ar-H),6.39(d,J＝8.0Hz,1H,＝CH),2.54(s,3H,CH 3 ),2.38(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.2,157.5,140.5,137.4,129.4,126.4,126.1,21.2,16.1；IR(neat):v＝3030,2923,2856,2751,1653,1604,1443,1375,1323,1251,1192,1145cm -1 ；MS(70eV,EI)m/z(％):160(M + ,15.56),145(100).
Example 4
A reaction formula (4);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (6.3mg，0.01mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.8mg,1.5 mmol), 1a (70.1 mg,1.0 mmol), THF (5 mL), reacted for 10 hours to give E-3ad (151.5 mg, 86%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/dichloromethane=2/1): yellow solid; melting point: 43.9-44.8deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.15(d,J＝8.0Hz,1H,CHO),7.54(d,J＝8.8Hz,2H,Ar-H),6.93(d,J＝8.4Hz,2H,Ar-H),6.38(d,J＝7.6Hz,1H,＝CH),3.84(s,3H,OCH 3 ),2.54(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.1,161.3,156.9,132.3,127.8,125.5,114.0,55.3,16.0；IR(neat):v＝2939,2842,2771,1650,1593,1512,1438,1376,1328,1285,1260,1245,1183,1146,1061,1025cm -1 ；MS(70eV,EI)m/z(％):176(M + ,100).
example 5
A reaction formula (5);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (6.3mg，0.01mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-bromophenylboronic acid (2E, 308.0mg,1.5 mmol), 1a (70.2 mg,1.0 mmol), THF (5 mL), reaction for 23.9 h gave E-3ae (183.5 mg, 81%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether, petroleum ether (containing 0.2% by volume of triethylamine)/dichloromethane=2/1): white solid; melting point: 41.3-42.4 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝8.0Hz,1H,CHO),7.54(d,J＝8.4Hz,2H,Ar-H),7.40(d,J＝8.4Hz,2H,Ar-H),6.36(d,J＝7.6Hz,1H,＝CH),2.54(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9,156.0,139.3,131.8,127.7,127.3,124.3,16.1；IR(neat):v＝2866,2777,1656,1610,1579,1482,1447,1396,1374,1320,1247,1075cm -1 ；MS(70eV,EI)m/z(％):226(M + ( 81 Br),15.98),224(M + ( 79 Br),17.51),145(100).
example 6
Reaction formula (6);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 3-bromophenylboronic acid (2 f,308.0mg,1.5 mmol), 1a (70.0 mg,1.0 mmol), THF (5 mL), reacted for 8 hours to give E-3af (182.4 mg, 81%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether, petroleum ether (containing 0.2% by volume of triethylamine)/dichloromethane=2/1): white solid; melting point: 71.0-71.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝7.6Hz,1H,CHO),7.66(s,1H,Ar-H),7.54(d,J＝7.6Hz,1H,Ar-H),7.46(d,J＝7.6Hz,1H,Ar-H),7.29(t,J＝8.0Hz,1H,Ar-H),6.34(d,J＝7.6Hz,1H,＝CH),2.54(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9,155.7,142.7,132.8,130.2,129.3,127.8,124.8,122.9,16.3；IR(neat):v＝3055,2861,1653,1553,1470,1440,1398,1374,1321,1244,1142,1060cm -1 ；MS(70eV,EI)m/z(％):226(M + ( 81 Br),5.59),224(M + ( 79 Br),6.44),183(100).
Example 7
A reaction formula (7);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.5mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 3-chlorobenzeneboronic acid (2 g,242.7mg, 97% purity, 1.5 mmol), 1a (71.0 mg,1.0 mmol), THF (5 mL) were reacted for 12 hours to give E-3ag (122.9 mg, 68%) (silica gel was basified with petroleum ether containing 5% volume fraction of triethylamine) (eluent: petroleum ether (containing 0.2% volume fraction of triethylamine)/ethyl acetate=20/1): yellow solid; melting point: 74.1-74.7deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝7.6Hz,1H,CHO),7.50(s,1H,Ar-H),7.46-7.30(m,3H,Ar-H),6.35(d,J＝7.6Hz,1H,＝CH),2.55(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9,155.7,142.4,134.7,129.9,129.8,127.8,126.4,124.3,16.3；IR(neat):v＝3059,2858,1653,1613,1561,1474,1441,1417,1376,1323,1246,1145,1103,1068cm -1 ；MS(70eV,EI)m/z(％):182(M( 37 Cl) + ,11.41),180(M( 35 Cl) + ,33.21),145(100).
example 8
Reaction type (8)
The procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.3 mg,0.05 mmol), 4-fluorobenzeneboronic acid (2 h,214.7mg,1.5 mmol), 1a (69.8 mg,1.0 mmol), THF (5 mL), reaction for 8.5 h gave E-3ah (100.9 mg,61%, purity 99%) (silica gel was basified with petroleum ether containing 5% volume fraction of triethylamine) (eluent: petroleum ether (containing 0.2% volume fraction of triethylamine)/ethyl acetate=20/1-15/1-10/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝7.6Hz,1H,CHO),7.54(dd,J 1 ＝7.6Hz,J 2 ＝5.6Hz,2H,Ar-H),7.10(t,J＝8.4Hz,2H,Ar-H),6.35(d,J＝7.6Hz,1H,＝CH),2.56(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.0,163.8(d,J＝248.9Hz),156.2,136.5(d,J＝3.2Hz),128.2(d,J＝8.7Hz),127.0,115.7(d,J＝21.4Hz),16.3； 19 F NMR(376MHz,CDCl 3 ):δ＝-111.0；IR(neat):v＝2854,1718,1656,1598,1507,1441,1412,1376,1231,1143cm -1 ；MS(70eV,EI)m/z(％):164(M + ,55.69),163(100).
example 9
A reaction formula (9);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 4-trifluoromethylphenylboronic acid (2 i,291.1mg,1.5 mmol), 1a (69.8 mg,1.0 mmol), THF (5 mL) were reacted for 17 hours to give E-3ai (144.8 mg, 68%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/ethyl acetate=20/1-10/1): yellow solid; melting point: 38.8-39.2 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝7.6Hz,1H,CHO),7.66(q,J＝8.5Hz,4H,Ar-H),6.39(d,J＝8.0Hz,1H,＝CH),2.59(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.8,155.6,144.2,131.5(q,J＝32.4Hz),128.4,126.5,125.6(q,J＝3.7Hz),123.7(q,J＝270.4Hz),16.3； 19 F NMR(376MHz,CDCl 3 ):δ＝-63.3；IR(neat):v＝2859,1660,1616,1448,1413,1376,1321,1167,1115,1074,1055,1012cm -1 ；MS(70eV,EI)m/z(％):214(M + ,17.33),69(100).
Example 10
A reaction formula (10);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.5mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O(10.1mg，0.05mmol)，4Acetylphenylboronic acid (2 j,251.5mg,1.5 mmol), 1a (70.9 mg,1.0 mmol), THF (5 mL), for 13 hours (silica gel basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/ethyl acetate=15/1-10/1-5/1): white solid; melting point: 78.5-79.7deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.21(d,J＝8.0Hz,1H,CHO),8.00(d,J＝8.4Hz,2H,Ar-H),7.63(d,J＝8.4Hz,2H,Ar-H),6.42(d,J＝7.6Hz,1H,＝CH),2.63(s,3H,CH 3 ),2.60(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝197.2,190.9,155.9,144.9,137.8,128.6,128.3,126.4,26.6,16.3；IR(neat):v＝3049,2968,2870,1647,1606,1422,1401,1357,1325,1265,1133,1057cm -1 ；MS(70eV,EI)m/z(％):188(M + ,97.5),145(100)；Anal.Calcd.for C 12 H 12 O 2 :C76.57,H6.43；foundC76.27,H6.51.
example 11
A reaction formula (11);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-methoxycarbonylphenylboronic acid (2 k,275.6mg,1.5 mmol), 1a (70.0 mg,1.0 mmol), THF (5 mL) were reacted for 6 hours to give E-3ak (148.8 mg, 73%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/ethyl acetate=10/1): orange solid; melting point: 87.7-89.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝7.6Hz,1H,CHO),8.07(d,J＝8.4Hz,2H,Ar-H),7.60(d,J＝8.4Hz,2H,Ar-H),6.40(d,J＝7.6Hz,1H,＝CH),3.94(s,3H,OCH 3 ),2.59(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9,166.2,156.0,144.8,131.1,129.8,128.2,126.1,52.2,16.2；IR(neat):v＝1721,1653,1614,1428,1275,1188,1143,1107,1013cm -1 ；MS(70eV,EI)m/z(％):204(M + ,8.82),145(100)；Anal.Calcd.for C 12 H 12 O 3 :C 70.58,H 5.92；found:C 70.56,H 5.85.
example 12
Reactive (12)
The procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (6.4mg，0.01mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 3-cyanophenylboronic acid (2 l,224.7mg,1.5 mmol), 1a (70.1 mg,1.0 mmol), THF (5 mL), reaction for 12.5 hours gave E-3al (121.1 mg, 71%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether (containing 0.2% by volume of triethylamine)/ethyl acetate=5/1, petroleum ether/ethyl acetate=5/1): yellow solid; melting point: 125.7-127.1 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝7.6Hz,1H,CHO),7.82(s,1H,Ar-H),7.77(d,J＝8.0Hz,1H,Ar-H),7.71(d,J＝7.6Hz,1H,Ar-H),7.56(t,J＝7.8Hz,1H,Ar-H),6.37(d,J＝7.2Hz,1H,＝CH),2.59(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.7,154.5,141.9,133.0,130.4,129.8,129.7,128.4,118.1,113.1,16.3；IR(neat):v＝3063,3035,2862,2226,1660,1615,1482,1421,1406,1382,1330,1261,1186,1173,1140cm -1 ；MS(70eV,EI)m/z(％):171(M + ,64.53),170(100).
Example 13
A reaction formula (13);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 3-nitrobenzoic acid (2 m,255.8mg,1.5 mmol), 1a (70.0 mg,1.0 mmol), THF (5 mL), reacted for 7 hours to give E-3am (119.5 mg, 63%) (first column chromatography: silica gel basified with 5% volume fraction triethylamine in petroleum ether, eluent: petroleum ether/dichloromethane=1/1. Second column chromatography: eluent: petroleum ether/dichloromethane=1/2.): a pale yellow solid; melting point: 134.8-135.1 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.22(d,J＝7.2Hz,1H,CHO),8.40(s,1H,Ar-H),8.28(d,J＝8.0Hz,1H,Ar-H),7.88(d,J＝8.0Hz,1H,Ar-H),7.64(t,J＝8.0Hz,1H,Ar-H),6.44(d,J＝7.6Hz,1H,＝CH),2.64(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.7,154.3,148.5,142.3,132.0,129.8,128.6,124.4,121.1,16.4；IR(neat):v＝3064,2880,1658,1606,1512,1475,1381,1350,1330,1281,1247,1146,1110cm -1 ；MS(70eV,EI)m/z(％):191(M + ,26.02),115(100).
example 14
A reaction formula (14);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-biphenylboronic acid (2 n,303.4mg,1.5 mmol), 1a (69.9 mg,1.0 mmol), THF (5 mL), reacted for 7 hours to give E-3an (155.6 mg, 70%) (first column chromatography: silica gel basified with 5% volume fraction triethylamine in petroleum ether, eluent: petroleum ether/dichloromethane=5/1-3/1. Second column chromatography: eluent: petroleum ether/ethyl acetate=30/1.): yellow solid; melting point: 125.9-127.1 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝7.6Hz,1H,CHO),7.69-7.57(m,6H,Ar-H),7.46(t,J＝7.6Hz,2H,Ar-H),7.38(t,J＝7.4Hz,1H,Ar-H),6.47(d,J＝7.6Hz,1H,＝CH),2.61(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.2,157.0,142.9,140.0,139.2,128.9,127.9,127.3,127.03,126.98,126.8,16.2；IR(neat):v＝2869,1647,1596,1485,1444,1411,1323,1244,1214,1136,1060,1001cm -1 ；MS(70eV,EI)m/z(％):222(M + ,100).
example 15
A reaction formula (15);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 2-naphthalene boronic acid (2O, 263.3mg,1.5 mmol), 1a (70.7 mg,1.0 mmol), THF (5 mL), reacted for 7 hours to give E-3ao (150.8 mg, 76%) (eluent: petroleum ether/ethyl acetate=25/1-20/1): yellow solid; melting point: 46.4-47.2 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.23(d,J＝8.0Hz,1H,CHO),8.01(s,1H,Ar-H),7.92-7.78(m,3H,Ar-H),7.63(d,J＝8.8Hz,1H,Ar-H),7.57-7.47(m,2H,Ar-H),6.54(d,J＝8.0Hz,1H,＝CH),2.65(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.1,157.1,137.5,133.9,132.9,128.6,128.3,127.5,127.4,127.1,126.6,126.2,123.3,16.2；IR(neat):v＝3058,1674,1641,1606,1506,1436,1382,1348,1317,1274,1219,1196,1150,1138,1123,1065cm -1 ；MS(70eV,EI)m/z(％):196(M + ,100).
Example 16
A reaction formula (16);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.4 mg,0.05 mmol), 3-furanboronic acid (2 p,174.4mg,1.5 mmol), 1a (70.3 mg,1.0 mmol), THF (5 mL), and E-3ap (97.0 mg, 71%) were obtained after 12 hours of reaction (elution)The preparation method comprises the following steps: petroleum ether/ethyl acetate=10/1-5/1): a pale yellow solid; melting point: 67.3-68.3 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.14(d,J＝8.0Hz,1H,CHO),7.78(s,1H,Furan-H),7.46(s,1H,Furan-H),6.62(s,1H,Furan-H),6.27(d,J＝7.6Hz,1H,＝CH),2.46(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.8,148.6,144.4,142.6,127.6,124.8,107.3,15.2；IR(neat):v＝3147,3124,2926,2880,1670,1615,1511,1421,1372,1328,1169,1152,1096,1072,1022cm -1 ；MS(70eV,EI)m/z(％):136(M + ,63.77),79(100)；Anal.Calcd.for C 8 H 8 O 2 :C 70.58,H 5.92；found:C 70.45,H 6.04.
example 17
Equation (17);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 2-thiopheneboronic acid (2 q,195.6mg,1.5 mmol), 1a (70.6 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3aq (96.3 mg, 63%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether/ethyl acetate=20/1): a red liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.11(d,J＝7.6Hz,1H,CHO),7.43(s,2H,Thiophene-H),7.14-7.03(m,1H,Thiophene-H),6.45(d,J＝7.6Hz,1H,＝CH),2.57(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.5,149.8,144.4,128.9,128.3,127.8,124.3,16.0；IR(neat):v＝2990,2901,1653,1599,1575,1513,1421,1380,1358,1326,1246,1219,1149,1127,1081,1057cm -1 ；MS(70eV,EI)m/z(％):152(M + ,100)；HRMS calcd m/z for C 8 H 8 OS[M + ]:152.0290,found:152.0290.
example 18
A reaction formula (18);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 3-thiopheneboronic acid (2 r,195.1mg,1.5 mmol), 1a (70.0 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3ar (112.4 mg, 74%) (eluent: petroleum ether/ethyl acetate=20/1-10/1): yellow solid; melting point: recrystallizing at 64.0-65.0deg.C (petroleum ether/dichloromethane); 1 H NMR(400MHz,CDCl 3 ):δ＝10.18(d,J＝7.6Hz,1H,CHO),7.66-7.58(m,1H,Thiophene-H),7.40-7.31(m,2H,Thiophene-H),6.43(d,J＝8.0Hz,1H,＝CH),2.54(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.4,150.9,142.2,126.7,125.59,125.57,125.1,15.9；IR(neat):v＝3102,3087,1643,1607,1511,1444,1416,1368,1309,1256,1195,1141,1098,1071cm -1 ；MS(70eV,EI)m/z(％):152(M + ,100)；Anal.Calcd.for C 8 H 8 OS:C 63.13,H 5.30；found:C 62.88,H 5.48.
example 19
A reaction formula (19);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.3 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,233.0mg,1.5 mmol), 1b (146.6 mg,1.0 mmol), THF (5 mL), reacted for 13 hours to give E-3bd (177.0 mg, 70%) (eluent: petroleum ether/diethyl ether/dichloromethane=20/1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.98(d,J＝7.2Hz,2H,Ar-H),7.59-7.49(m,3H,Ar-H),7.49-7.41(m,2H,Ar-H),7.16(s,1H,＝CH),6.93(d,J＝8.8Hz,2H,Ar-H),3.83(s,3H,OCH 3 ),2.60(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.7,160.6,154.8,139.6,134.8,132.3,128.4,128.1,127.9,120.2,113.9,55.3,18.6；IR(neat):v＝3062,2957,2837,1651,1597,1585,1566,1511,1447,1378,1277,1250,1211,1176,1047,1025cm -1 ；MS(70eV,EI)m/z(％):252(M + ,80.28),251(100).
example 20
A reaction formula (20);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (16.0mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.5mg,1.5 mmol), 1c (159.8 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3cd (228.0 mg, 86%) (eluent: petroleum ether/diethyl ether/dichloromethane=20/1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.56(d,J＝7.6Hz,1H,Ar-H),7.51(d,J＝8.4Hz,2H,Ar-H),7.33(t,J＝7.2Hz,1H,Ar-H),7.28-7.19(m,2H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),6.87(s,1H,＝CH),3.81(s,3H,OCH 3 ),2.58(s,3H,CH 3 ),2.51(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝195.9,160.6,153.9,141.0,136.9,134.4,131.4,130.4,128.1,127.8,125.5,123.4,113.8,55.2,20.4,18.2；IR(neat):v＝2957,2931,2837,1654,1583,1564,1511,1455,1435,1377,1288,1250,1211,1179,1129,1030cm -1 ；MS(70eV,EI)m/z(％):266(M + ,39.88),251(100)；HRMS calcd m/z for C 18 H 18 O 2 [M + ]:266.1301,found:266.1301.
example 21
A reaction formula (21);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.3mg,1.5 mmol), 1d (159.9 mg,1.0 mmol), THF (5 mL), and the reaction time of 12 hours gave E-3dd (227.6 mg, 86%) (eluent: petroleum ether/diethyl ether/dichloromethane=20/1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.85-7.70(m,2H,Ar-H),7.53(d,J＝8.4Hz,2H,Ar-H),7.40-7.25(m,2H,Ar-H),7.14(s,1H,＝CH),6.92(d,J＝8.8Hz,2H,Ar-H),3.81(s,3H,OCH 3 ),2.58(s,3H,CH 3 ),2.40(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.8,160.5,154.3,139.6,138.1,134.7,133.0,128.6,128.2,127.8,125.3,120.4,113.8,55.2,21.3,18.4；IR(neat):v＝2957,2837,1651,1582,1566,1511,1437,1377,1278,1238,1177,1161,1030cm -1 ；MS(70eV,EI)m/z(％):266(M + ,75.62),251(100)；HRMS calcd m/z for C 18 H 18 O 2 [M + ]:266.1301,found:266.1302.
example 22
A reaction formula (22);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.9mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,233.0mg,1.5 mmol), 1E (160.5 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3ed (230.2 mg, 86%) (eluent: petroleum ether/diethyl ether/dichloromethane=30/1/1): yellow solid; melting point: 53.1-53.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.89(d,J＝7.6Hz,2H,Ar-H),7.53(d,J＝8.4Hz,2H,Ar-H),7.24(d,J＝7.2Hz,2H,Ar-H),7.14(s,1H,＝CH),6.91(d,J＝8.4Hz,2H,Ar-H),3.81(s,3H,OCH 3 ),2.57(s,3H,CH 3 ),2.38(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.3,160.4,154.0,142.9,137.0,134.8,129.1,128.2,127.7,120.3,113.8,55.2,21.5,18.4；IR(neat):v＝3042,2958,2838,1649,1604,1584,1511,1431,1416,1276,1252,1220,1204,1177,1048,1021cm -1 ；MS(70eV,EI)m/z(％):266(M + ,38.68),251(100)；Anal.Calcd.for C 18 H 18 O 2 :C 81.17,H 6.81；found C 80.78,H 7.09.
Example 23
A reaction formula (23);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.6mg，0.025mmol)，NaOAc(16.3mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.2mg,1.5 mmol), 1f (225.7 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3fd (274.4 mg, 83%) (eluent: petroleum ether/diethyl ether/dichloromethane=25/1/1-20/1/1): yellow solid; melting point: 110.0-110.8deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.85(d,J＝8.4Hz,2H,Ar-H),7.60(d,J＝8.4Hz,2H,Ar-H),7.55(d,J＝8.4Hz,2H,Ar-H),7.10(s,1H,＝CH),6.94(d,J＝8.8Hz,2H,Ar-H),3.86(s,3H,OCH 3 ),2.60(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.3,160.7,155.8,138.4,134.6,131.7,129.7,127.9,127.3,119.5,113.9,55.3,18.7；IR(neat):v＝3010,2960,2838,1647,1582,1507,1456,1346,1260,1206,1181,1067,1028,1004cm -1 ；MS(70eV,EI)m/z(％):332(M + ( 81 Br),48.84),330(M + ( 79 Br),50.27),251(100)；Anal.Calcd.for C 17 H 15 BrO 2 :C 61.65,H 4.57；found C 61.65,H 4.77.
example 24
A reaction formula (24);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.5mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.2mg,1.5 mmol), 1g (196.7 mg,1.0 mmol), THF (5 mL), and E-3gd (248.0 mg, 82%) (eluent: petroleum ether/diethyl ether/dichloromethane=20/1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.50(d,J＝8.4Hz,1H,Ar-H),7.92(d,J＝8.0Hz,1H,Ar-H),7.85(d,J＝8.0Hz,1H,Ar-H),7.79(d,J＝7.2Hz,1H,Ar-H),7.61-7.40(m,5H,Ar-H),7.01(s,1H,＝CH),6.88(d,J＝8.8Hz,2H,Ar-H),3.78(s,3H,OCH 3 ),2.66(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝195.4,160.6,154.4,139.0,134.3,133.8,131.5,130.1,128.4,127.9,127.3,127.0,126.2,125.6,124.6,123.9,113.9,55.2,18.4；IR(neat):v＝3048,2957,2837,1652,1580,1562,1508,1461,1436,1375,1280,1250,1224,1174,1104,1029cm -1 ；MS(70eV,EI)m/z(％):302(M + ,100)；HRMS calcd m/z for C 21 H 18 O 2 [M + ]:302.1301,found:302.1303.
example 25
Equation (25);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 4-formylphenylboronic acid (2 s,229.4mg,1.5 mmol), 1h (152.4 mg,1.0 mmol), THF (5 mL), reaction for 21 h afforded E-3hs (208.8 mg, 81%) (eluent: petroleum ether/ethyl acetate=30/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.04(s,1H,CHO),7.90(d,J＝8.0Hz,2H,Ar-H),7.65(d,J＝8.0Hz,2H,Ar-H),6.62(s,1H,＝CH),2.54(s,3H,CH 3 ),2.51-2.41(m,1H,CH),1.99-1.88(m,2H,CH 2 ),1.85-1.75(m,2H,CH 2 ),1.73-1.59(m,1H,one proton of CH 2 ),1.48-1.12(m,5H,one proton of CH 2 and 2 x CH 2 )； 13 C NMR(100MHz,CDCl 3 ):δ＝204.0,191.3,151.8,148.5,136.1,129.6,126.9,125.2,51.9,28.3,25.7,25.5,18.0；IR(neat):v＝2927,2852,1700,1677,1599,1566,1449,1373,1308,1212,1171,1145,1094,1065cm -1 ；MS(70eV,EI)m/z(％):256(M + ,24.1),173(100)；HRMS calcd m/z for C 17 H 20 O 2 [M + ]:256.1458,found:256.1465.
example 26
Equation (26);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.3 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.9mg,1.5 mmol), 1i (140.5 mg,1.0 mmol), THF (5 mL), reacted for 12 hours to give E-3id (174.3 mg, 71%) (eluent: petroleum ether/dichloromethane=3/1-2/1): white solid; melting point: 42.2-43.0deg.C (petroleum ether recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.47(d,J＝8.8Hz,2H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),6.48(s,1H,＝CH),3.83(s,3H,OCH 3 ),2.58-2.47(m,5H,CH 2 andCH 3 ),1.65(quint,J＝7.2Hz,2H,CH 2 ),1.40-1.24(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.4,160.4,152.9,134.5,127.7,122.5,113.8,55.2,44.8,31.4,24.0,22.4,17.9,13.8；IR(neat):v＝2953,2931,2860,1675,1588,1569,1512,1425,1371,1294,1250,1182,1130,1084,1032cm -1 ；MS(70eV,EI)m/z(％):246(M + ,9.14),175(100)；Anal.Calcd.for C 16 H 22 O 2 :C 78.01,H 9.00；found C 77.97,H9.05.
Example 27
Reaction formula (27);
the operation is the same as that of the practiceExample 1.[ Cp ] RhCl 2 ] 2 (15.4mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.4 mg,0.05 mmol), 4-cyanophenylboronic acid (2 t,231.9mg,1.5 mmol), 1j (194.4 mg,1.0 mmol), THF (5 mL), reacted for 38 hours to give E-3jt (236.5 mg,81%, purity 98%) (eluent: petroleum ether/ethyl acetate=25/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.68(d,J＝8.4Hz,2H,Ar-H),7.58(d,J＝8.4Hz,2H,Ar-H),6.50(s,1H,＝CH),5.10(t,J＝6.6Hz,1H,＝CH),2.62-2.44(m,4H,one proton of CH 2 and CH 3 ),2.41-2.30(m,1H,one proton of CH 2 ),2.15-1.90(m,3H,CHandCH 2 ),1.67(s,3H,CH 3 ),1.60(s,3H,CH 3 ),1.43-1.31(m,1H,one proton of CH 2 ),1.31-1.18(m,1H,one proton of CH 2 ),0.96(d,J＝6.4Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.0,150.7,147.0,132.2,131.3,127.0,126.4,124.2,118.3,112.3,52.2,36.9,29.3,25.6,25.3,19.7,17.9,17.5；IR(neat):v＝2962,2914,2874,2853,2228,1683,1602,1557,1504,1437,1405,1377,1278,1116,1060cm -1 ；MS(70eV,EI)m/z(％):295(M + ,5.18),170(100)；HRMS calcd m/z for C 20 H 25 NO[M + ]:295.1931,found:295.1935.
example 28
A reaction formula (28);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 1-pentenylboronic acid (2 u,175.0mg,1.5 mmol), 1d (160.1 mg,1.0 mmol), THF (5 mL), reaction for 12 hours afforded (E, E) -3du (137.9 mg, 60%) (eluent: petroleum ether/ethyl acetate=40/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.78-7.64(m,2H,Ar-H),7.32(d,J＝4.4Hz,2H,Ar-H),6.74(s,1H,＝CH),6.30-6.16(m,2H,2 x CH),2.40(s,3H,CH 3 ),2.31(s,3H,CH 3 ),2.19(q,J＝6.5Hz,2H,CH 2 ),1.56-1.43(m,2H,CH 2 ),0.95(t,J＝7.4Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝192.2,152.3,139.6,138.3,138.1,134.5,133.0,128.6,128.2,125.2,122.7,35.2,22.2,21.3,14.7,13.7；IR(neat):v＝2959,2928,2872,1653,1630,1603,1575,1435,1360,1261,1161,1067,1049cm -1 ；MS(70eV,EI)m/z(％):228(M + ,15.38),185(100)；HRMS calcd for C 16 H 20 O[M + ]:228.1514,found:228.1512.
example 29
A reaction formula (29);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), cyclopropylboronic acid (2 v,132.0mg,1.5 mmol), 1c (160.3 mg,1.0 mmol), THF (5 mL), reacted for 15 hours to give E-3cv (159.6 mg, 80%) (eluent: petroleum ether/ethyl acetate=40/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.48(d,J＝7.2Hz,1H,Ar-H),7.30(t,J＝7.4Hz,1H,Ar-H),7.21(t,J＝7.2Hz,2H,Ar-H),6.47(s,1H,＝CH),2.45(s,3H,CH 3 ),2.00(s,3H,CH 3 ),1.64-1.54(m,1H,CH),0.90-0.80(m,2H,CH 2 ),0.80-0.72(m,2H,CH 2 )； 13 C NMR(100MHz,CDCl 3 ):δ＝195.2,161.8,141.1,136.6,131.2,130.1,127.8,125.4,122.1,20.6,20.3,15.5,7.3；IR(neat):v＝3014,2964,2927,1656,1586,1456,1432,1242,1206,1038,1018cm -1 ；MS(70eV,EI)m/z(％):200(M + ,22.57),185(100)；HRMS calcd for C 14 H 16 O[M] + :200.1196,found:200.1204.
example 30
A reaction formula (30);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), cyclopropylboronic acid (2 v,132.0mg,1.5 mmol), 1i (140.3 mg,1.0 mmol), THF (5 mL), reacted for 15 hours to give E-3iv (139.3 mg, 77%) (eluent: petroleum ether/ethyl acetate=40/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 )δ＝6.12(s,1H,＝CH),2.40(t,J＝7.4Hz,2H,CH 2 ),1.94(s,3H,CH 3 ),1.65-1.54(m,2H,CH 2 ),1.54-1.47(m,1H,CH),1.38-1.21(m,4H,2 x CH 2 ),0.89(t,J＝6.8Hz,3H,CH 3 ),0.84-0.74(m,2H,CH 2 ),0.74-0.68(m,2H,CH 2 )； 13 C NMR(100MHz,CDCl 3 ,)δ＝200.7,160.1,121.4,44.4,31.5,24.1,22.5,20.3,15.1,13.9,6.9；IR(neat):v＝3012,2956,2930,2860,1681,1599,1459,1397,1368,1132,1059cm -1 ；MS(70eV,EI)m/z(％):180(M + ,2.52),81(100)；HRMS calcdfor C 12 H 20 O[M] + :180.1509,found:180.1514.
Example 31
A reaction formula (31);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), methylboronic acid (2 w,93.0mg,1.5 mmol), 1d (160.2 mg,1.0 mmol), THF (5 mL), were reacted for 12 hours to give E-3dw (101.3 mg, 58%) (first column chromatography: eluent: petroleum ether, petroleum ether/ethyl acetate=50/1, 63.7mg of pure product and some of the impure product. Second column chromatography: eluent: petroleum ether, petroleum ether/ethyl acetate=100/1, 37.6mg of pure product): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.78-7.66(m,2H,Ar-H),7.33(d,J＝4.4Hz,2H,Ar-H),6.73(s,1H,＝CH),2.40(s,3H,CH 3 ),2.20(s,3H,CH 3 ),2.01(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.7,156.2,139.3,138.1,133.0,128.7,128.3,125.3,121.4,27.9,21.3,21.1；IR(neat):v＝2975,2914,2861,1660,1614,1600,1585,1442,1378,1259,1172,1156,1020cm -1 ；MS(70eV,EI)m/z(％):174(M + ,49.76),159(100)；HRMS calcd for C 12 H 14 O[M + ]:174.1045,found:174.1043.
example 32
A reaction formula (32);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.5mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.3 mg,0.05 mmol), 3-methoxyphenylboronic acid (2 a,234.7mg,1.5 mmol), 1k (145.9 mg,1.0 mmol), THF (5 mL), reacted for 27 hours to give E-3ka (166.2 mg, 66%) (first column chromatography: eluent: petroleum ether/ethyl acetate=40/1-10/1, to give a partially pure product and some impure product. Second column chromatography: eluent: petroleum ether/ethyl acetate=50/1, to give another partially pure product): a pale yellow solid; melting point: 61.1-61.9 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝10.19(d,J＝7.6Hz,1H,CHO),7.33-7.22(m,3H,Ar-H),7.22-7.15(m,3H,Ar-H),7.08(d,J＝7.6Hz,1H,Ar-H),7.00(s,1H,Ar-H),6.90(dd,J 1 ＝8.2Hz,J 2 ＝2.2Hz,1H,Ar-H),6.52(d,J＝8.0Hz,1H,＝CH),4.38(s,2H,CH 2 ),3.76(s,3H,OCH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.4,159.7,159.0,141.1,137.7,129.7,128.80,128.77,128.1,126.7,119.3,115.4,112.6,55.2,35.7；IR(neat):v＝3024,2955,2830,1648,1599,1573,1491,1426,1287,1137,1050cm -1 ；MS(70eV,EI)m/z(％):252(M + ,100)；Anal.Calcd.for C 17 H 16 O 2 :C 80.93,H 6.39；found C 81.17,H 6.31.
example 33
A reaction formula (33);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.7mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 2-biphenylboronic acid (2O, 263.2mg,1.5 mmol), 1l (159.9 mg,1.0 mmol), THF (5 mL) were reacted for 22 hours to give E-3lo (150.3 mg, 53%) (first column chromatography: eluent: petroleum ether/ethyl acetate=50/1-20/1. Second column chromatography: eluent: petroleum ether/ethyl acetate=60/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝8.0Hz,1H,CHO),7.94(s,1H,Ar-H),7.83-7.64(m,3H,Ar-H),7.54(d,J＝8.4Hz,1H,Ar-H),7.48-7.33(m,2H,Ar-H),7.08(d,J＝7.2Hz,2H,Ar-H),7.01(d,J＝7.2Hz,2H,Ar-H),6.63(d,J＝7.6Hz,1H,＝CH),4.39(s,2H,CH 2 ),2.21(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.2,159.1,136.7,136.2,134.7,133.8,132.9,129.4,128.7,128.6,128.4,127.9,127.4,127.1,127.0,126.5,123.9,35.0,20.8；IR(neat):v＝2921,2856,1655,1604,1572,1452,1386,1274,1138cm -1 ；MS(70eV,EI)m/z(％):286(M + ,100)；HRMS calcd m/z for C 21 H 18 O[M + ]:286.1352,found:286.1358.
example 34
A reaction formula (34);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.7mg，0.025mmol)，NaOAc(16.7mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.5 mg,0.05 mmol), phenylboronic acid (2 b,186.9mg,1.5 mmol), 1m (152.2 mg,1.0 mmol), THF (5 mL), were reacted for 24 hours to give E-3mb (132.9 mg, 58%) (eluent: petroleum ether/ethyl acetate=40/1): pale yellow liquid； 1 H NMR(400MHz,CDCl 3 ):δ＝10.16(d,J＝7.6Hz,1H,CHO),7.59-7.45(m,2H,Ar-H),7.40-7.29(m,3H,Ar-H),7.26-7.17(m,1H,Thiophene-H),6.96-6.79(m,2H,Thiophene-H),6.48(d,J＝7.6Hz,1H,＝CH),4.35(s,2H,CH 2 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.1,158.8,139.5,138.1,130.0,128.7,127.9,127.5,126.7,126.1,121.6,30.8；IR(neat):v＝2921,2851,1658,1608,1572,1493,1445,1287,1137,1080cm -1 ；MS(70eV,EI)m/z(％):228(M + ,100)；HRMS calcd m/z for C 14 H 12 OS[M + ]:228.0603,found:228.0603.
Example 35
A reaction formula (35);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.4mg，0.025mmol)，NaOAc(16.6mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.5 mg,0.05 mmol), 3-methylphenylboronic acid (2X, 204.1mg,1.5 mmol), 1n (214.0 mg,1.0 mmol), THF (5 mL) were reacted for 22 hours to give the crude product (E-3 nx with 60% nuclear magnetic yield). A Schlenk tube was taken, the crude product and methanol (5 mL) were added, cooled to 0℃with an ice-water bath, and then NaBH was added 4 (115.9 mg,3.0 mmol). The mixture was stirred at 0deg.C for 1.5h, then water (15 mL) and ethyl acetate (15 mL) were added and the organic solvent was removed by rotary evaporation. Subsequently, the mixture was extracted with ethyl acetate (15 ml×3), and the organic phase was washed with saturated aqueous sodium chloride solution, then dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Separation and purification by silica gel column chromatography (eluent: petroleum ether/ethyl acetate=30/1-15/1-5/1) gave product E-8nx (174.0 mg, 57%): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.46(d,J＝8.0Hz,2H,Ar-H),7.24(d,J＝7.6Hz,2H,Ar-H),7.19-7.08(m,3H,Ar-H),7.04(d,J＝6.8Hz,1H,Ar-H),6.16(t,J＝6.6Hz,1H,＝CH),4.35(d,J＝6.8Hz,2H,CH 2 ),3.92(s,2H,CH 2 ),2.29(s,3H,CH 3 ),1.86(s,1H,OH)； 13 C NMR(100MHz,CDCl 3 ):δ＝143.4,141.4,139.6,138.0,129.1,128.41(q,J＝32.1Hz),128.38,128.35,128.3,127.1,125.4(q,J＝3.7Hz),124.2(q,J＝270.2Hz),123.4,59.8,35.7,21.4； 19 F NMR(376MHz,CDCl 3 ):δ＝-62.9；IR(neat):v＝3024,2920,2861,1618,1601,1581,1485,1416,1323,1106,1067cm -1 ；MS(70eV,EI)m/z(％):306(M + ,25.00),119(100)；HRMS calcd m/z for C 18 H 17 F 3 O[M + ]:306.1226,found:306.1230.
Example 36
A reaction formula (36);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.6mg，0.025mmol)，NaOAc(16.7mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 4-methoxyphenylboronic acid (2 d,232.7mg,1.5 mmol), 1O (112.0 mg,1.0 mmol), THF (5 mL), and reacted for 16 hours to give E-3od (153.0 mg, 70%) (eluent: petroleum ether/ethyl acetate=30/1-20/1): a pale yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.12(d,J＝8.0Hz,1H,CHO),7.48(d,J＝8.8Hz,2H,Ar-H),6.93(d,J＝8.8Hz,2H,Ar-H),6.28(d,J＝8.0Hz,1H,＝CH),3.83(s,3H,OCH 3 ),3.01(t,J＝7.6Hz,2H,CH 2 ),1.57-1.45(m,2H,CH 2 ),1.38(sextet,J＝7.4Hz,2H,CH 2 ),0.90(t,J＝7.2Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.8,162.5,161.1,131.5,128.0,125.9,114.1,55.2,32.3,29.2,22.5,13.6；IR(neat):v＝2958,2931,2860,2838,1657,1596,1568,1511,1462,1286,1243,1180,1144,1104,1030cm -1 ；MS(70eV,EI)m/z(％):218(M + ,93.60),148(100)；HRMS calcd m/z for C 14 H 18 O 2 [M + ]:218.1301,found:218.1305.
example 37
A reaction formula (37);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.5mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.2 mg,0.05 mmol), 4-cyanophenylboronic acid (2 t,231.9mg,1.5 mmol), (6S) -1j (193.1 mg,1.0 mmol), THF (5 mL) were reacted for 22 hours to give (S) -E-3jt (226.0 mg,77%,96% ee) (eluent: petroleum ether/ethyl acetate=25/1-20/1): a yellow liquid; HPLCconditions AD-H column, hexane/i-PrOH=97/3, 1.0mL/min, λ=214 nm, t R (minor)＝8.7min,t R (major)＝9.2min；[α] 25 D ＝+5.98(c＝1.01,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝7.68(d,J＝8.4Hz,2H,Ar-H),7.57(d,J＝8.0Hz,2H,Ar-H),6.50(s,1H,＝CH),5.09(t,J＝6.4Hz,1H,＝CH),2.62-2.45(m,4H,one proton of CH 2 and CH 3 ),2.42-2.30(m,1H,one proton of CH 2 ),2.15-1.90(m,3H,CHandCH 2 ),1.67(s,3H,CH 3 ),1.60(s,3H,CH 3 ),1.42-1.31(m,1H,one proton of CH 2 ),1.31-1.18(m,1H,one proton of CH 2 ),0.95(d,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.1,150.7,147.0,132.2,131.4,127.1,126.5,124.2,118.4,112.3,52.2,36.9,29.4,25.6,25.4,19.7,17.9,17.5；IR(neat):v＝2961,2917,2875,2864,2229,1683,1602,1439,1406,1377,1279,1059cm -1 ；MS(70eV,EI)m/z(％):295(M + ,5.77),170(100)；HRMS calcd m/z for C 20 H 25 NO[M + ]:295.1931,found:295.1931.
Example 38
A reaction formula (38);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (77.6mg，0.125mmol)，NaOAc(82.2mg，1.0mmol)，Cu(OAc) 2 ·H 2 O (50.2 mg,0.25 mmol), 4-methoxyphenylboronic acid [ (B-E-G)2d,1.1637g,7.5 mmol), 1f (1.1257 g,5.0 mmol), THF (25 mL), for 22 hours to give E-3fd (1.2669, 76%) (first column chromatography: eluent: petroleum ether, petroleum ether/ethyl acetate=30/1 gives a partially pure product and some impure product. The impure product was subjected to a second column chromatography: eluent: petroleum ether/diethyl ether/dichloromethane=25/1/1): yellow solid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.84(d,J＝8.4Hz,2H,Ar-H),7.59(d,J＝8.4Hz,2H,Ar-H),7.54(d,J＝8.4Hz,2H,Ar-H),7.09(s,1H,＝CH),6.93(d,J＝8.4Hz,2H,Ar-H),3.84(s,3H,OCH 3 ),2.60(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝190.3,160.7,155.8,138.4,134.6,131.7,129.7,127.9,127.3,119.5,113.9,55.3,18.7.
Example 39
A reaction formula (39);
a dry Schlenk tube was taken, protected by argon, and a solution of E-3ad (88.4 mg,0.5 mmol) in THF (1 mL) was added at room temperature followed by slow (4 min) dropwise addition of ethyl magnesium bromide (1.0 mol/LinTHF,0.8mL,0.8 mmol) at-20deg.C. After the completion of the dropwise addition, the mixture was stirred at-20℃for 10min, and then returned to room temperature for further stirring for 1 hour. The mixture was successively added with saturated aqueous ammonium chloride (1 mL) and water (5 mL), extracted with ethyl acetate (5 mL. Times.3), and the organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. Separation and purification by silica gel column chromatography (eluent: petroleum ether/ethyl acetate=10/1-5/1) gave product E-4 (89.2 mg, 86%): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.34(d,J＝8.4Hz,2H,Ar-H),6.85(d,J＝8.8Hz,2H,Ar-H),5.68(d,J＝8.4Hz,1H,＝CH),4.44(q,J＝7.1Hz,1H,CH),3.79(s,3H,OCH 3 ),2.06(s,3H,CH 3 ),1.92(s,1H,OH),1.77-1.63(m,1H,one proton of CH 2 ),1.63-1.48(m,1H,one proton of CH 2 ),0.94(t,J＝7.4Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝158.8,136.4,135.4,129.1,126.8,113.5,70.3,55.2,30.5,16.2,9.7；IR(neat):v＝3363,2961,2932,2875,2836,1607,1511,1462,1287,1245,1180,1032cm -1 ；MS(70eV,EI)m/z(％):206(M + ,45.75),135(100)；HRMS calcd m/z for C 13 H 18 O 2 [M + ]:206.1301,found:206.1302.
example 40
A reaction formula (40);
a dry Schlenk tube was taken, purged with argon, and a solution of ethyl acetate (88.4 mg, d=0.902 g/mL, 98. Mu.L, 1.0 mmol) in THF (1 mL) was added at room temperature followed by slow (3 min) dropwise addition of LDA solution (2.0 mol/LinTHF,0.5mL,1.0 mmol) at-78 ℃. The mixture was stirred at-78deg.C for 10min, then a solution of E-3ad (88.9 mg,0.5 mmol) in THF (1 mL) was slowly (5 min) added dropwise at-78deg.C. After the completion of the dropwise addition, stirring was continued at-78℃for 2 hours. The mixture was successively added with saturated aqueous ammonium chloride (2 mL) and water (5 mL), extracted with ethyl acetate (5 mL. Times.3), and the organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. Separation and purification by silica gel column chromatography (eluent: petroleum ether/ethyl acetate=5/1-3/1) gave product E-5 (121.9 mg, 91%): a yellow liquid; 1 H NMR(400MHz,CDCl3):δ＝7.32(d,J＝8.4Hz,2H,Ar-H),6.84(d,J＝8.4Hz,2H,Ar-H),5.72(d,J＝8.4Hz,1H,＝CH),5.03-4.88(m,1H,CH),4.17(q,J＝7.1Hz,2H,CH 2 ),3.78(s,3H,OCH 3 ),3.15(s,1H,OH),2.64(dd,J 1 ＝15.8Hz,J 2 ＝8.2Hz,1H,one proton of CH 2 ),2.56(dd,J 1 ＝16.0Hz,J 2 ＝4.0Hz,1H,one proton of CH 2 ),2.07(s,3H,CH 3 ),1.26(t,J＝7.0Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl3):δ＝172.3,159.0,137.2,135.0,126.9,126.7,113.5,65.5,60.7,55.2,41.6,16.2,14.1；IR(neat):v＝3281,2987,2959,2827,2839,1730,1647,1605,1512,1443,1281,1244,1180,1159,1101,1023cm -1 ；MS(70eV,EI)m/z(％):264(M + ,23.54),135(100).
Example 41
A reaction formula (41);
a Schlenk tube was taken and E-3ad (88.4 mg,0.5 mmol) and ethoxyformylmethylene triphenylphosphine (355.5 mg,1.0 mmol) were added successively at room temperature and dichloromethane (2 mL) and the mixture stirred at 25℃for 33h. The reaction solution was filtered through a short column of silica gel, washed with ethyl acetate (5 mL. Times.4), and the solvent was removed by rotary evaporation. Separation and purification by silica gel column chromatography (eluent: petroleum ether/ethyl acetate=25/1-15/1) gave the product (E, E) -6 (105.6 mg, 85%): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.75(dd,J 1 ＝14.8Hz,J 2 ＝12.0Hz,1H,CH),7.44(d,J＝8.4Hz,2H,Ar-H),6.88(d,J＝8.4Hz,2H,Ar-H),6.53(d,J＝11.6Hz,1H,＝CH),5.94(d,J＝15.2Hz,1H,＝CH),4.23(q,J＝7.2Hz,2H,CH 2 ),3.81(s,3H,OCH 3 ),2.26(s,3H,CH 3 ),1.31(t,J＝7.2Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝167.5,159.8,144.7,140.9,134.1,127.1,123.0,120.3,113.8,60.1,55.2,16.3,14.3；IR(neat):v＝2984,2961,2841,1703,1620,1598,1568,1511,1462,1443,1364,1297,1249,1178,1142,1026cm -1 ；MS(70eV,EI)m/z(％):246(M + ,47.62),173(100)；HRMS calcd m/z for C 15 H 18 O 3 [M + ]:246.1250,found:246.1250.
example 42
A reaction formula (42);
taking a Schlenk tube, adding Pd at room temperature 2 (dba) 3 ·CHCl 3 (13.1 mg,0.0127 mmol), triphenylphosphine (6.5 mg,0.025 mmol), E-3fd (165.9 mg,0.5 mmol), phenylboronic acid (2 b,124.0mg,1.0 mmol), cesium carbonate (162.6 mg,0.5 mmol).The Schlenk tube was evacuated three times, purged with argon, and then toluene (1 mL) was added. The mixture was stirred at 80℃for 43h, allowed to return to room temperature, and then quenched with water (1 mL). Water (5 mL) was further added, extracted with dichloromethane (5 mL. Times.3), and the organic phase was washed with saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. Separation and purification by silica gel column chromatography (eluent: petroleum ether/diethyl ether/dichloromethane=40/1/1-30/1/1) gave product E-7 (141.6 mg, 86%): yellow solid; melting point: 115.8-116.3 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝8.06(d,J＝7.6Hz,2H,Ar-H),7.68(d,J＝7.6Hz,2H,Ar-H),7.62(d,J＝7.2Hz,2H,Ar-H),7.56(d,J＝8.0Hz,2H,Ar-H),7.51-7.41(m,2H,Ar-H),7.41-7.32(m,1H,Ar-H),7.20(s,1H,＝CH),6.94(d,J＝8.0Hz,2H,Ar-H),3.83(s,3H,OCH 3 ),2.61(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl3):δ＝191.1,160.6,154.7,145.0,140.0,138.3,134.8,128.9,128.7,128.0,127.9,127.2,127.1,120.2,113.9,55.3,18.6；IR(neat):v＝3005,2956,2837,1646,1587,1506,1457,1411,1347,1255,1214,1180,1028cm -1 ；MS(70eV,EI)m/z(％):328(M + ,100)；Anal.Calcd.for C 23 H 20 O 2 :C 84.12,H 6.14；found C 84.00,H 6.22.
Example 43
A reaction formula (43);
a Schlenk tube was taken and E-3fd (331.1 mg,1.0 mmol), methanol (5 mL) were added sequentially at room temperature, then cooled to 0deg.C with an ice-water bath, and sodium borohydride (154.6 mg,4.0 mmol) was added. The mixture was stirred at 0deg.C for 30min, brought to room temperature, water (20 mL) and ethyl acetate (20 mL) were added and the organic solvent was removed by rotary evaporation. Subsequently, the mixture was extracted with ethyl acetate (20 ml×3), and the organic phase was washed with saturated aqueous sodium chloride solution, then dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. Purification by recrystallization (petroleum ether/dichloromethane) afforded product E-8fd (302.1 mg, 91%): white solidA body; melting point: recrystallizing at 96.5-97.4deg.C (petroleum ether/dichloromethane); 1 H NMR(400MHz,CDCl 3 ):δ＝7.47(d,J＝8.0Hz,2H,Ar-H),7.40-7.22(m,4H,Ar-H),6.85(d,J＝8.4Hz,2H,Ar-H),5.86(d,J＝8.4Hz,1H,＝CH),5.59(d,J＝8.4Hz,1H,CH),3.80(s,3H,OCH 3 ),2.17(s,3H,CH 3 ),1.97(brs,1H,OH)； 13 C NMR(100MHz,CDCl 3 ):δ＝159.1,142.7,137.0,134.8,131.5,128.0,127.7,126.9,121.2,113.6,70.4,55.2,16.4；IR(neat):v＝3196,2957,2838,1605,1511,1464,1443,1403,1289,1251,1179,1070,1028,1006cm -1 ；MS(70eV,EI)m/z(％):334(M + ( 81 Br),38.68),332(M + ( 79 Br),38.80),135(100)；Anal.Calcd.for C 17 H 17 79 BrO 2 :C61.28,H5.14；found:C60.77,H 5.35；HRMS calcd m/z for C 17 H 17 79 BrO 2 [M + ]:332.0406,found:332.0412.
example 44
A reaction formula (44);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 4-methoxyphenylboronic acid (2 d,116.3mg,0.75 mmol), 1p-d 1 (77.7 mg,0.5mmol, deuteration)>99%) THF (2.5 mL) and reacted for 12 hours to give E-3pd-d 1 (111.9 mg,86%, deuteration 99%) (eluent: petroleum ether/ethyl acetate=20/1): a pale yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.6(d,J＝8.8Hz,2H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),6.48(s,1H,Ar-H),3.82(s,3H,OCH 3 ),2.55-2.45(m,4H,CH 2 and CH 2 D),1.70-1.55(m,2H,CH 2 ),1.49-1.21(m,6H,3 x CH 2 ),0.94-0.83(m,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.5,160.4,152.8,134.6,127.8,122.6,113.8,55.2,44.9,31.6,28.9,24.4,22.5,17.7(t,J＝19.4Hz),14.0；IR(neat):v＝2954,2928,2856,1680,1589,1570,1511,1463,1420,1368,1290,1251,1180,1130,1075,1033cm -1 ；MS(70eV,EI)m/z(％):261(M + ,11.06),176(100)；HRMS calcd m/z for C 17 H 23 DO 2 [M + ]:261.1834,found:261.1834.
example 45
Equation (45);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.4mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.1 mg,0.025 mmol), 2-naphthaleneboronic acid (2O, 131.6mg,0.75 mmol), 1a-d 2 (36.4 mg,0.5mmol, deuteration 96%) THF (2.5 mL) was reacted for 18 hours to give E-3ao-d 2 (80.5 mg, 80%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether/ethyl acetate=15/1): yellow solid; melting point: 46.3-47.1 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝8.00(s,1H,Ar-H),7.91-7.71(m,3H,Ar-H),7.61(d,J＝8.8Hz,1H,Ar-H),7.56-7.37(m,2H,Ar-H),6.53(s,1H,＝CH),2.61(s,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9(t,J＝26.0Hz),157.1,137.5,133.9,132.9,128.6,128.4,127.6,127.4(t,J＝3.6Hz),127.2,126.7,126.3,123.3,16.0(t,J＝19.8Hz)；IR(neat):v＝3056,3035,2130,1650,1624,1598,1505,1358,1267,1195,1163cm -1 ；MS(70eV,EI)m/z(％):198(M + ,100)；HRMS calcd m/z for C 14 H 10 D 2 O[M + ]:198.1008,found:198.1009.
example 46
A reaction formula (46);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.3 mg,0.025 mmol), 3-furanboronic acid (2 p,87.5mg,0.75 mmol), 1a-d 2 (37.8 mg,0.5mmol, deuteration 96%) THF (2.5 mL) was reacted for 12 hours to give E-3ap-d 2 (50.0 mg, 69%) (eluent: petroleum ether/ethyl acetate=15/1-5/1): a pale brown solid; melting point: 69.7-70.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.77(s,1H,Furan-H),7.46(s,1H,Furan-H),6.62(s,1H,Furan-H),6.28(s,1H,＝CH),2.45-2.37(m,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝190.5(t,J＝26.0Hz),148.6,144.4,142.6,127.6,124.8(t,J＝3.6Hz),107.4,15.1(t,J＝19.4Hz)；IR(neat):v＝3148,3123,2924,2130,1657,1651,1609,1512,1333,1175,1159cm -1 ；MS(70eV,EI)m/z(％):138(M + ,76.95),81(100)；HRMS calcd m/z for C 8 H 6 D 2 O 2 [M + ]:138.0644,found:138.0640.
example 47
A reaction formula (47);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.3mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.3 mg,0.025 mmol), 3-thiopheneboronic acid (2 r,97.8mg,0.75 mmol), 1a-d 2 (36.9 mg,0.5mmol, deuteration 96%) THF (2.5 mL) was reacted for 12 hours to give E-3ar-d 2 (57.1 mg, 72%) (eluent: petroleum ether/ethyl acetate=20/1-15/1-5/1): yellow solid; melting point: 66.7-67.3deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.62(s,1H,Thiophene-H),7.42-7.29(m,2H,Thiophene-H),6.43(s,1H,＝CH),2.54-2.42(m,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝191.1(t,J＝25.9Hz),150.9,142.2,126.7,125.6,125.5,125.1,15.7(t,J＝19.7Hz)；IR(neat):v＝3102,3086,2131,1626,1599,1508,1416,1315,1248,1165cm -1 ；MS(70eV,EI)m/z(％):154(M + ,100)；HRMS calcd m/z for C 8 H 6 D 2 OS[M + ]:154.0416,found:154.0414.
example 48
Equation (48);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.5mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.3 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.3mg, 97% pure, 0.75 mmol), 1a-d 2 (36.2 mg,0.5mmol, deuteration 96%) THF (2.5 mL) was reacted for 18 hours to give E-3aa-d 2 (73.4 mg, 82%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether/ethyl acetate=20/1-15/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.32(t,J＝8.2Hz,1H,Ar-H),7.13(d,J＝7.6Hz,1H,Ar-H),7.07-7.02(m,1H,Ar-H),6.96(dd,J 1 ＝8.2Hz,J 2 ＝2.2Hz,1H,Ar-H),6.38(s,1H,＝CH),3.83(s,3H,OCH 3 ),2.54-2.46(m,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝190.9(t,J＝26.1Hz),159.7,157.4,142.0,129.7,127.2(t,J＝3.6Hz),118.6,115.4,111.9,55.3,16.1(t,J＝19.4Hz)；IR(neat):v＝2922,2837,2106,1647,1601,1574,1487,1427,1260,1157,1036cm -1 ；MS(70eV,EI)m/z(％):178(M + ,90.99),147(100)；HRMS calcd m/z for C 11 H 10 D 2 O 2 [M + ]:178.0957,found:178.0959.
example 49
Equation (49);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.1 mg,0.025 mmol), 3-chlorobenzoic acid (2 g,120.7mg, 97% purity, 0.75 mmol), 1a-d 2 (36.8 mg,0.5mmol, deuteration 96%) THF (2.5 mL) was reacted for 6 hours to give E-3ag-d 2 (72.9 mg, 78%) (silica gel was basified with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether/ethyl acetate=15/1): yellow solid; melting point: 75.3-75.8 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.51(s,1H,Ar-H),7.46-7.29(m,3H,Ar-H),6.35(s,1H,＝CH),2.59-2.42(m,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝190.6(t,J＝26.0Hz),155.7,142.4,134.8,129.9,129.8,127.8(t,J＝3.6Hz),126.4,124.3,16.0(t,J＝19.4Hz)；IR(neat):v＝3059,2114,1647,1632,1560,1410,1337,1238,1163,1082cm -1 ；MS(70eV,EI)m/z(％):184(M( 37 Cl) + ,9.54),182(M( 35 Cl) + ,29.11),147(100)；HRMS calcd m/z for C 10 H 8 D 2 35 ClO[M+H] + :183.0540,found 183.0536.
example 50
A reaction formula (50);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.3 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.2mg, purity 97%,0.75 mmol), 1g-d 1 (117.3 mg, purity 84%,0.5mmol, deuteration rate)>99%) THF (2.5 mL) was reacted for 16 hours to give E-3ga-d 1 (123.1 mg,81%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.54(d,J＝8.4Hz,1H,Ar-H),7.92(d,J＝8.0Hz,1H,Ar-H),7.85(d,J＝8.0Hz,1H,Ar-H),7.83-7.77(m,1H,Ar-H),7.59-7.52(m,1H,Ar-H),7.52-7.42(m,2H,Ar-H),7.27(t,J＝8.0Hz,1H,Ar-H),7.13(d,J＝7.6Hz,1H,Ar-H),7.07(t,J＝1.8Hz,Ar-H),7.03(s,1H,＝CH),6.89(dd,J 1 ＝8.0Hz,J 2 ＝2.0Hz,1H,Ar-H),3.78(s,3H,OCH 3 ),2.63-2.58(m,2H,CH 2 D)； 13 C NMR(100MHz,CDCl 3 ):δ＝195.4,159.6,154.5,143.9,138.4,133.8,131.8,130.1,129.5,128.4,127.41,127.39,126.2,125.7,125.6,124.5,118.9,114.3,112.4,55.2,18.5(t,J＝19.4Hz)；IR(neat):v＝3048,2833,1655,1572,1485,1429,1287,1227,1175,1103cm -1 ；MS(70eV,EI)m/z(％):303(M + ,100)；HRMS calcd m/z for C 21 H 17 DO 2 [M + ]:303.1364,found:303.1365.
Example 51
A reaction formula (51);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.6mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.1 mg,0.025 mmol), 4-cyanophenylboronic acid (2 t,116.0mg, 95% purity, 0.75 mmol), 1d-d 1 (80.8 mg,0.5mmol, deuteration)>99%) THF (2.5 mL) and reacted for 15 hours to give E-3dt-d 1 (92.0 mg,70%, deuteration 98%) (eluent: petroleum ether/ethyl acetate=30/1-20/1): yellow solid; melting point: 69.7-71.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.83-7.74(m,2H,Ar-H),7.71(d,J＝8.4Hz,2H,Ar-H),7.65(d,J＝8.0Hz,2H,Ar-H),7.42-7.33(m,2H,Ar-H),7.14(s,1H,＝CH),2.54-2.48(m,2H,CH 2 D),2.43(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.7,151.5,147.0,138.6,138.4,133.7,132.3,128.7,128.5,127.0,125.5,124.5,118.4,112.3,21.3,18.2(t,J＝19.8Hz)；IR(neat):v＝3058,2855,2226,1650,1582,1411,1254,1157cm -1 ；MS(70eV,EI)m/z(％):262(M + ,66.11),247(100)；HRMS calcd m/z for C 18 H 14 DNO[M + ]:262.1211,found:262.1210.
example 52
A reaction formula (52);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.4mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.2 mg,0.025 mmol), 4-methoxyphenylboronic acid (2 d,117.4mg, purity 97%,0.75 mmol), 1i-d 1 (70.9 mg,0.5mmol, deuteration)>99%) THF (2.5 mL) and reacted for 12 hours to give E-3id-d 1 (99.8 mg,80%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a pale yellow solid; melting point: 42.6-43.5 ℃ (petroleum ether recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.46(d,J＝8.8Hz,2H,Ar-H),6.90(d,J＝9.2Hz,2H,Ar-H),6.48(s,1H,＝CH),3.83(s,3H,OCH 3 ),2.58-2.42(m,4H,CH 2 and CH 2 D),1.65(quint,J＝7.4Hz,2H,CH 2 ),1.44-1.19(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.5,160.4,152.9,134.6,127.8,122.6,113.8,55.3,44.9,31.5,24.1,22.5,17.8(t,J＝19.4Hz),13.9；IR(neat):v＝2953,2931,2859,1675,1584,1565,1454,1371,1082cm -1 ；MS(70eV,EI)m/z(％):247(M + ,11.53),176(100)；HRMS calcd m/z for C 16 H 21 DO 2 [M + ]:247.1677,found:247.1676.
example 53
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A reaction formula (53);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (8.1mg，0.0125mmol)，NaOAc(8.5mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.3 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,118.0mg, 97% pure, 0.75 mmol), 1g-d 2 (98.7mg，0.5mmol，Deuteration rate>99%) THF (2.5 mL) was reacted for 34.5 hours to give E-3ga-d 2 (124.3 mg,82%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.54(d,J＝8.4Hz,1H,Ar-H),7.93(d,J＝8.0Hz,1H,Ar-H),7.86(d,J＝8.4Hz,1H,Ar-H),7.82(d,J＝6.8Hz,1H,Ar-H),7.56(t,J＝7.2Hz,1H,Ar-H),7.52-7.40(m,2H,Ar-H),7.28(t,J＝8.0Hz,1H,Ar-H),7.13(d,J＝8.0Hz,1H,Ar-H),7.10-7.05(m,1H,Ar-H),7.03(s,1H,＝CH),6.90(dd,J 1 ＝8.2Hz,J 2 ＝1.8Hz,1H,Ar-H),3.79(s,3H,OCH 3 ),2.59(s,1H,CHD 2 )； 13 C NMR(100MHz,CDCl 3 ):δ＝195.4,159.6,154.4,143.9,138.4,133.8,131.8,130.1,129.5,128.4,127.4,126.3,125.8,125.6,124.5,118.9,114.3,112.4,55.2,18.2(quint,J＝19.6Hz)；IR(neat):v＝3050,2834,1654,1571,1486,1429,1287,1228,1175,1104cm -1 ；MS(70eV,EI)m/z(％):304(M + ,100)；HRMS calcd m/z for C 21 H 16 D 2 O 2 [M + ]:304.1427,found:304.1424.
Example 54
A reaction formula (54);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.3mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 4-cyanophenylboronic acid (2 t,115.8mg, 95% pure, 0.75 mmol), 1d-d 2 (80.9 mg,0.5mmol, deuteration)>99%) THF (2.5 mL) and reacted for 36 hours to give E-3dt-d 2 (86.5 mg,66%, deuteration rate)>99%) (first, separating and purifying by silica gel column chromatography: eluent: petroleum ether/dichloromethane=3/1-2/1. Then recrystallized (petroleum ether/dichloromethane) for further purification): yellow solid; melting point: 73.1-73.6deg.C (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.82-7.62(m,2H,Ar-H),7.71(d,J＝8.0Hz,2H,Ar-H),7.65(d,J＝8.4Hz,2H,Ar-H),7.45-7.32(m,2H,Ar-H),7.15(s,1H,＝CH),2.50(s,1H,CHD 2 ),2.43(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.7,151.5,147.0,138.6,138.5,133.7,132.3,128.8,128.5,127.1,125.5,124.5,118.5,112.4,21.3,17.9(quint,J＝19.6Hz)；IR(neat):v＝3059,2918,2227,1650,1581,1412,1254,1158cm -1 ；MS(70eV,EI)m/z(％):263(M + ,61.84),248(100)；HRMS calcd m/z for C 18 H 13 D 2 NO[M + ]:263.1274,found:263.1267.
example 55
A reaction formula (55);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (8.0mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.2 mg,0.025 mmol), 4-methoxyphenylboronic acid (2 d,118.0mg, purity 97%,0.75 mmol), 1i-d 2 (70.1 mg,0.5mmol, deuteration)>99%) THF (2.5 mL) and reacted for 12 hours to give E-3id-d 2 (95.7 mg,78%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a pale yellow solid; melting point: 41.6-42.5 ℃ (petroleum ether recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.46(d,J＝8.8Hz,2H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),6.49(s,1H,＝CH),3.83(s,3H,OCH 3 ),2.61-2.38(m,3H,CH 2 and CHD 2 ),1.65(quint,J＝7.2Hz,2H,CH 2 ),1.43-1.20(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.5,160.4,152.8,134.6,127.8,122.6,113.8,55.3,44.9,31.5,24.1,22.5,17.5(quint,J＝19.6Hz),13.9；IR(neat):v＝2953,2931,2860,1674,1583,1563,1454,1371,1082cm -1 ；MS(70eV,EI)m/z(％):248(M + ,12.31),177(100)；HRMS calcd m/z for C 16 H 20 D 2 O 2 [M + ]:248.1740,found:248.1745.
example 56
A reaction formula (56);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.5mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.4 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.4mg, purity 97%,0.75 mmol), 1g-d 3 (99.0 mg,0.5mmol, deuteration) >99%) THF (2.5 mL) and reacted for 44 hours to give E-3ga-d 3 (123.9 mg,82%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.54(d,J＝8.4Hz,1H,Ar-H),7.94(d,J＝8.4Hz,1H,Ar-H),7.86(d,J＝8.0Hz,1H,Ar-H),7.82(d,J＝6.8Hz,1H,Ar-H),7.62-7.40(m,3H,Ar-H),7.29(t,J＝8.0Hz,1H,Ar-H),7.14(d,J＝7.6Hz,1H,Ar-H),7.08(t,J＝2.0Hz,1H,Ar-H),7.04(s,1H,＝CH),6.91(dd,J 1 ＝8.2Hz,J 2 ＝1.8Hz,1H,Ar-H),3.80(s,3H,OCH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝195.4,159.6,154.4,143.9,138.4,133.8,131.8,130.2,129.5,128.4,127.45,127.43,126.3,125.8,125.6,124.5,118.9,114.3,112.4,55.2,18.0(hept,J＝19.6Hz)；IR(neat):v＝3050,2834,1653,1570,1486,1429,1289,1228,1175,1104cm -1 ；MS(70eV,EI)m/z(％):305(M + ,100)；HRMS calcd m/z for C 21 H 15 D 3 O 2 [M + ]:305.1490,found:305.1492.
example 57
A reaction formula (57);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.4mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 4-cyanophenylboronic acid (2 t,115.6mg, 95% pure, 0.75 mmol), 1d-d 3 (82.2mg，0.5mmol, deuteration rate>99%) THF (2.5 mL) and reacted for 15 hours to give E-3dt-d 3 (92.7 mg,70%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=30/1-15/1): yellow solid; melting point: 69.7-71.7 ℃ (petroleum ether/dichloromethane recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.85-7.74(m,2H,Ar-H),7.71(d,J＝8.0Hz,2H,Ar-H),7.65(d,J＝8.0Hz,2H,Ar-H),7.46-7.33(m,2H,Ar-H),7.14(s,1H,＝CH),2.43(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.7,151.4,146.9,138.6,138.4,133.7,132.3,128.7,128.4,127.0,125.5,124.5,118.4,112.3,21.3,17.6(hept,J＝20.3Hz)；IR(neat):v＝3058,2855,2226,1650,1579,1412,1270,1158cm -1 ；MS(70eV,EI)m/z(％):264(M + ,67.24),249(100)；HRMS calcd m/z for C 18 H 12 D 3 NO[M + ]:264.1336,found:264.1332.
example 58
A reaction formula (58);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.8mg，0.0125mmol)，NaOAc(8.1mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.1 mg,0.025 mmol), 4-methoxyphenylboronic acid (2 d,117.9mg, purity 97%,0.75 mmol), 1i-d 3 (72.2 mg,0.5mmol, deuteration rate)>99%) THF (2.5 mL) and reacted for 12 hours to give E-3id-d 3 (101.4 mg,81% deuteration)>99%) (eluent: petroleum ether/ethyl acetate=30/1): a pale yellow solid; melting point: 40.7-42.5 ℃ (petroleum ether recrystallization); 1 H NMR(400MHz,CDCl 3 ):δ＝7.46(d,J＝8.8Hz,2H,Ar-H),6.90(d,J＝8.8Hz,2H,Ar-H),6.49(s,1H,＝CH),3.83(s,3H,OCH 3 ),2.52(t,J＝7.4Hz,2H,CH 2 ),1.64(quint,J＝7.3Hz,2H,CH 2 ),1.42-1.23(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.5,160.4,152.8,134.5,127.8,122.6,113.8,55.2,44.8,31.4,24.1,22.5,17.2(hept,J＝19.4Hz),13.9；IR(neat):v＝2954,2931,2858,1673,1583,1564,1454,1371,1079cm -1 ；MS(70eV,EI)m/z(％):249(M + ,14.32),178(100)；HRMS calcd m/z for C 16 H 19 D 3 O 2 [M + ]:249.1803,found:249.1806.
example 59
Reaction formula (59);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O(2.1mg，0.01mmol)，2y(89.4mg，0.3mmol)，1i-d 3 (28.9 mg,0.2mmol, deuteration)>99%) THF (1 mL) was reacted for 20 hours to give E-3iy-d 3 (41.9 mg,52%, deuteration rate)>99%) (eluent: petroleum ether/ethyl acetate=50/1-30/1): a liquid; [ alpha ]] 24 D ＝+88.41(c＝0.97,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝7.35-7.25(m,2H,Ar-H),7.23(s,1H,Ar-H),6.50(s,1H,＝CH),3.02-2.92(m,2H,CH 2 ),2.60-2.40(m,4H),2.39-2.28(m,1H),2.23-1.92(m,4H),1.75-1.41(m,8H),1.40-1.21(m,4H),0.96-0.81(m,6H)； 13 C NMR(100MHz,CDCl 3 ):δ＝220.6,201.7,153.2,141.0,140.0,136.6,127.0,125.5,123.8,123.6,50.4,47.9,44.9,44.4,38.0,35.8,31.5,31.4,29.4,26.4,25.6,24.0,22.5,21.5,17.4(hept,J＝19.6Hz),13.9,13.8；IR(neat):v＝2928,2858,1737,1679,1586,1558,1499,1454,1407,1372,1290,1130,1073,1007cm -1 ；MS(ESI)m/z:396.3(M+H) + ；HRMS calcd m/z for C 27 H 34 D 3 O 2 [(M+H) + ]:396.2976,found:396.2970.
Example 60
A reaction formula (60);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.4mg，0.04mmol)，Cu(OAc) 2 ·H 2 O(2.1mg，0.01mmol)，2aa(121.6mg，0.3mmol)，1d-d 3 (31.8 mg,0.2mmol, deuteration)>99%) THF (1 mL) was reacted for 20 hours to give E-3daa-d 3 (84.5 mg,83%, deuteration rate)>99%) (eluent: petroleum ether/diethyl ether/dichloromethane=5/1/1): a pale yellow liquid; [ alpha ]] 26 D ＝-26.27(c＝1.05,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝8.08(d,J＝8.0Hz,2H,Ar-H),7.83-7.76(m,2H,Ar-H),7.64(d,J＝8.4Hz,2H,Ar-H),7.44-7.36(m,2H,Ar-H),7.18(s,1H,＝CH),5.98(d,J＝3.6Hz,1H,OCH),5.53(d,J＝2.0Hz,1H,OCH),4.66(d,J＝3.6Hz,1H,OCH),4.42-4.31(m,2H),4.18-4.08(m,2H),2.43(s,3H,CH 3 ),1.57(s,3H,CH 3 ),1.43(s,3H,CH 3 ),1.34(s,3H,CH 3 ),1.29(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.9,164.7,152.5,147.6,138.9,138.4,133.6,130.0,129.7,128.8,128.5,126.6,125.5,124.1,112.4,109.4,105.1,83.3,79.9,76.7,72.5,67.2,26.8,26.7,26.2,25.2,21.3,17.8(hept,J＝19.6Hz)；IR(neat):v＝2988,2936,2896,1724,1656,1605,1590,1564,1373,1264,1215,1184,1164,1094,1073,1016cm -1 ；MS(70eV,EI)m/z(％):525(M + ,2.25),266(100)；HRMS calcd m/z for C 30 H 31 D 3 O 8 [M + ]:525.2436,found:525.2436.
Example 61
A reaction formula (61);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.6mg, purity 97%,0.75 mmol), 1w-d 1 (148.4 mg, purity 95%,0.5mmol, deuteration rate)>99%) THF (2.5 mL) was reacted for 24 hours to giveE-3wa-d 1 (127.1 mg,66%, deuteration 97%) (silica gel was alkalized with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether, petroleum ether/ethyl acetate=50/1): a pale yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.32-7.27(m,2H,Ar-H),7.24(t,J＝7.4Hz,1H,Ar-H),7.04(d,J＝8.0Hz,2H,Ar-H),7.01-6.95(m,1H,Ar-H),6.90(t,J＝2.0Hz,1H,Ar-H),6.87(dd,J 1 ＝8.0Hz,J 2 ＝2.4Hz,1H,Ar-H),6.56(s,1H,＝CH),4.31(s,1H,CDH),3.77(s,3H,OCH 3 ),2.56(t,J＝7.4Hz,2H,CH 2 ),1.70-1.58(m,2H,CH 2 ),1.40-1.25(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.2,159.6,154.3,142.5,137.8,131.3,130.4,129.6,125.8,119.8,119.5,114.2,113.1,55.2,45.0,35.6(t,J＝19.8Hz),31.4,23.9,22.5,13.9；IR(neat):v＝3078,2988,2956,2924,2910,2901,1683,1594,1573,1485,1466,1430,1402,1365,1296,1287,1251,1240,1205,1172,1128,1072,1048,1013cm -1 ；MS(ESI)m/z:404[M( 81 Br)+H] + ,402[M( 79 Br)+H] + ；HRMS calcd m/z for C 22 H 25 D 79 BrO 2 [(M+H) + ]:402.1173,found:402.1175.
example 62
A reaction formula (62);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (7.7mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.6mg, purity 97%,0.75 mmol), 1w-d 2 (148.8 mg,0.5mmol, 99% deuteration) THF (2.5 mL) was reacted for 18 hours to give E-3wa-d 2 (145.5 mg,72%, deuteration 97%) (silica gel was alkalized with petroleum ether containing 5% by volume of triethylamine) (eluent: petroleum ether, petroleum ether/ethyl acetate=50/1): a pale yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.29(d,J＝8.4Hz,2H,Ar-H),7.24(t,J＝8.0Hz,1H,Ar-H),7.04(d,J＝8.4Hz,2H,Ar-H),6.98(d,J＝7.6Hz,1H,Ar-H),6.90(t,J＝2.0Hz,1H,Ar-H),6.86(dd,J 1 ＝8.0Hz,J 2 ＝2.4Hz,1H,Ar-H),6.56(s,1H,＝CH),3.77(s,3H,OCH 3 ),2.56(t,J＝7.4Hz,2H,CH 2 ),1.70-1.58(m,2H,CH 2 ),1.40-1.25(m,4H,2 x CH 2 ),0.90(t,J＝6.8Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.1,159.6,154.2,142.5,137.8,131.3,130.4,129.6,125.8,119.8,119.4,114.1,113.1,55.2,45.0,35.3(quint,J＝19.0Hz),31.4,23.8,22.5,13.9；IR(neat):v＝3078,2988,2955,2923,2872,1682,1592,1571,1485,1466,1458,1429,1395,1363,1288,1240,1204,1173,1128,1079,1070,1044,1013cm -1 ；MS(ESI)m/z:405[M( 81 Br)+H] + ,403[M( 79 Br)+H] + ；HRMS calcd m/z for C 22 H 24 D 2 79 BrO 2 [(M+H) + ]:403.1236,found:403.1234.
Example 63
A reaction formula (63);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.4mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.1 mg,0.01 mmol), 4-bromophenylboronic acid (2E, 60.8mg,0.3 mmol), 1p (78.1 mg,0.2 mmol), THF (1 mL), reacted for 17 hours to give E-3pe (99.7 mg, 91%) (eluent: petroleum ether, petroleum ether/ethyl acetate=25/1-20/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝7.65(d,J＝8.4Hz,2H,Ar-H),7.52-7.40(m,4H,Ar-H),7.26(d,J＝8.4Hz,2H,Ar-H),6.92(d,J＝2.8Hz,1H,Ar-H),6.86(d,J＝9.2Hz,1H,Ar-H)6.66(dd,J 1 ＝9.0Hz,J 2 ＝2.6Hz,1H,Ar-H),6.55(d,J＝0.8Hz,1H,＝CH),3.88-3.75(m,5H,CH 2 and OCH 3 ),2.51(d,J＝0.8Hz,CH 3 ),2.39(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝197.1,168.2,156.1,154.1,141.1,139.2,135.9,133.8,131.7,131.1,130.9,130.8,129.1,128.0,123.5,123.1,115.0,113.0,111.6,101.3,55.7,40.7,18.3,13.5；IR(neat):v＝2927,2832,1676,1594,1476,1455,1435,1399,1354,1313,1289,1260,1223,1178,1151,1087,1062,1035,1008cm -1 ；MS(ESI)m/z:536.1(M( 79 Br, 35 Cl)+H) + ；HRMS calcd m/z for C 28 H 23 BrClNO 3 [M( 79 Br, 35 Cl) + ]:535.0544,found:535.0548.
example 64
A reaction formula (64);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 4-methoxyphenylboronic acid (2 d,47.0mg, 97% pure, 0.3 mmol), 1q (75.3 mg,0.2 mmol), THF (1 mL) were reacted for 14 hours to give E-3qd (62.2 mg,62%, 97% pure) (eluent: petroleum ether, petroleum ether/ethyl acetate=10/1-5/1-3/1): a yellow liquid; [ alpha ]] 31 D ＝+24.66(c＝0.79,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝10.13(d,J＝7.6Hz,1H,CHO),7.48(d,J＝8.8Hz,2H,Ar-H),7.26-7.16(m,4H,Ar-H),6.88(d,J＝8.8Hz,2H,Ar-H),6.55(d,J＝7.6Hz,1H,＝CH),4.40(s,2H,CH 2 ),3.85-3.73(4H,OCH 3 and one proton of SCH 2 ),3.17(d,J＝15.2Hz,1H,one proton of SCH 2 ),2.58-2.47(m,1H,one proton of CH 2 ),2.47-2.36(dt,J 1 ＝18.8Hz,J 2 ＝3.9Hz,1H,one proton of CH 2 ),2.18-2.02(m,2H,CH and one proton of CH 2 ),1.96(d,J＝18.4Hz,1H,one proton of CH 2 ),1.76-1.64(m,1H,one proton of CH 2 ),1.50-1.40(m,1H,one proton of CH 2 ),1.14(s,3H,CH 3 ),0.89(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝214.0,190.9,161.4,157.5,147.8,137.1,130.9,129.5,128.5,126.9,122.3,114.3,58.0,55.3,47.9,47.5,42.7,42.4,34.5,26.8,25.0,19.8,19.6；IR(neat):v＝2962,2840,1744,1656,1597,1568,1502,1456,1370,1355,1246,1176,1143,1028cm -1 ；MS(ESI)m/z:483(M+H) + ；HRMS calcd m/z for C 27 H 31 O 6 S[(M+H) + ]:483.1836,found:483.1826.
Example 65
A reaction formula (65);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 4-methoxyphenylboronic acid (2 d,47.0mg, 97% purity, 0.3 mmol), 1r (87.3 mg,0.2 mmol), THF (1 mL) were reacted for 20 hours to give E-3rd (87.1 mg, 80%) (first column chromatography: eluent: toluene, toluene/acetone=50/1. Second column chromatography: petroleum ether/dichloromethane=1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝10.22(d,J＝8.0Hz,1H,CHO),7.92(s,1H,Ar-H),7.79(d,J＝8.4Hz,1H,Ar-H),7.75(d,J＝8.4Hz,1H,Ar-H),7.72-7.65(m,1H,Ar-H),7.61(s,1H,Ar-H),7.59-7.44(m,4H,Ar-H),7.34(d,J＝8.4Hz,1H,Ar-H),6.96(d,J＝8.4Hz,1H,Ar-H),6.84(d,J＝8.8Hz,2H,Ar-H),6.62(d,J＝8.0Hz,1H,＝CH),4.53(s,2H,CH 2 ),3.87(s,3H,OCH 3 ),3.76(s,3H,OCH 3 ),2.16(s,6H,3 x CH 2 ),2.09(s,3H,3 x CH),1.79(s,6H,3 x CH 2 )； 13 C NMR(100MHz,CDCl 3 ):δ＝191.4,161.2,158.5,158.2,138.9,138.8,135.2,133.0,132.6,132.3,131.3,128.63,128.57,127.9,127.1,126.7,126.3,126.1,125.8,125.5,124.7,114.2,112.0,55.3,55.1,40.6,37.12,37.09,35.5,29.1；IR(neat):v＝2900,2846,1656,1598,1568,1509,1494,1453,1440,1281,1235,1179,1140,1102,1029cm -1 ；MS(70eV,EI)m/z(％):542(M + ,100)；HRMS calcd m/z for C 38 H 38 O 3 [M + ]:542.2815,found:542.2820.
example 66
Equation (66);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 2y (89.6 mg,0.3 mmol), 1a (14.0 mg,0.2 mmol), THF (1 mL) was reacted for 24 hours to give E-3ay (51.9 mg, 81%) (eluent (0.2% volume percent triethylamine was added): petroleum ether/ethyl acetate=10/1-5/1): white solid; melting point: 160.7-161.1 ℃ (petroleum ether/ethyl acetate recrystallization); [ alpha ] ] 28 D ＝+155.76(c＝0.41,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝10.17(d,J＝8.0Hz,1H,CHO),7.40-7.28(m,3H,Ar-H),6.40(d,J＝8.0Hz,1H,＝CH),3.02-2.92(m,2H,CH 2 ),2.60-2.42(m,5H),2.39-2.28(m,1H),2.23-2.03(m,3H),2.03-1.95(m,1H),1.71-1.38(m,6H),0.92(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝220.5,191.2,157.5,142.2,137.9,136.9,126.9,126.6,125.7,123.6,50.4,47.8,44.4,37.9,35.7,31.5,29.4,26.3,25.5,21.5,16.2,13.7；IR(neat):v＝2958,2928,2914,2868,2856,1736,1651,1613,1595,1497,1439,1255,1180,1144,1134cm -1 ；MS(70eV,EI)m/z(％):322(M + ,100)；HRMS calcd m/z for C 22 H 26 O 2 [M + ]:322.1927,found:322.1926.
Example 67
A reaction formula (67);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (1.6mg，0.0026mmol)，NaOAc(1.7mg，0.02mmol)，Cu(OAc) 2 ·H 2 O (1.1 mg, 0.006mmol), 2z (95.2 mg,0.15 mmol), 1a (7.1 mg,0.1 mmol), THF (0.5 mL) reacted for 20 hours to give E-3az (40.7 mg, 61%) (eluent: petroleum)Ether/ethyl acetate=5/1-3/1-2/1): a pale yellow solid; melting point:>200℃；[α] 26 D ＝+117.29(c＝1.02,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝10.20(d,J＝7.6Hz,1H,CHO),8.08(d,J＝8.4Hz,2H,Ar-H),7.60(d,J＝8.4Hz,2H,Ar-H),6.41(d,J＝7.2Hz,1H,＝CH),5.69(s,1H,＝CH),4.81-4.75(m,1H,OCH),3.70(s,3H,OCH 3 ),2.92-2.83(m,1H),2.59(s,3H,CH 3 ),2.41(s,1H),2.15-0.85(m,37H),0.82(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝200.1,191.0,176.9,169.3,165.6,156.3,144.8,132.1,129.9,128.5,128.3,126.2,81.6,61.7,55.0,51.8,48.4,45.4,44.0,43.2,41.0,38.7,38.4,37.7,36.9,32.6,31.8,31.1,28.5,28.3,28.2,26.44,26.37,23.6,23.3,18.7,17.4,17.0,16.42,16.41；IR(neat):v＝2971,2947,2928,2865,1726,1660,1612,1448,1385,1320,1279,1262,1211,1198,1166,1143,1112,1016cm -1 ；MS(ESI)m/z:657.4(M+H) + ；HRMS calcd m/z for C 42 H 57 O 6 [(M+H) + ]:657.4150,found:657.4154.
example 68
A reaction formula (68);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 2aa (122.4 mg,0.3 mmol), 1s (80.1 mg,0.2 mmol), THF (1 mL), reaction for 24 hours gave E-3saa (122.0 mg, 80%) (eluent: petroleum ether, petroleum ether/ether=2/1-1/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.03(d,J＝8.4Hz,2H,Ar-H),7.55(d,J＝8.4Hz,2H,Ar-H),6.52(d,J＝1.2Hz,1H,＝CH),5.96(d,J＝3.6Hz,1H,OCH),5.51(d,J＝2.4Hz,1H,OCH),4.64(d,J＝3.6Hz,1H,OCH),4.41-4.29(m,2H,OCH 2 ),4.18-4.05(m,2H,OCH 2 ),3.68-3.57(m,1H,OCH),2.65-2.42(m,5H,CH 2 and CH 3 ),2.02-1.93(m,1H,CH),1.93-0.85(m,44H),0.65(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝201.9,164.7,151.7,147.7,129.9,129.6,126.6,125.8,112.4,109.4,105.1,83.3,79.9,72.5,71.8,67.2,56.5,56.0,42.7,42.0,41.8,40.4,40.1,36.4,35.8,35.33,35.29,34.5,30.5,30.1,28.2,27.1,26.8,26.7,26.4,26.2,25.2,24.2,23.3,20.8,18.5,18.2,12.0；IR(neat):v＝3494,2933,2864,1726,1682,1604,1447,1372,1262,1215,1164,1096,1068,1015cm -1 ；MS(ESI)m/z:785(M+Na) + ；HRMS calcd m/z for C 46 H 66 O 9 Na[(M+Na) + ]:785.4599,found:785.4589.
example 69
A reaction formula (69);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 2ab (70.6 mg,0.3 mmol), 1t (59.5 mg,0.2 mmol), THF (1 mL), reacted for 24 hours to give E-3tab (77.6 mg, 80%) (eluent: petroleum ether, petroleum ether/ethyl acetate=10/1): a yellow liquid; 1 H NMR(400MHz,CDCl 3 ):δ＝8.07(d,J＝8.4Hz,2H,Ar-H),7.57(d,J＝8.4Hz,2H,Ar-H),6.92(d,J＝1.2Hz,1H,＝CH),4.44(dd,J 1 ＝12.0Hz,J 2 ＝2.1Hz,1H,OCH),4.41-4.32(m,1H,OCH),4.27-4.12(m,2H,OCH 2 ),2.58(d,J＝0.8Hz,3H,CH 3 ),2.50-2.31(m,2H,CH 2 ),1.95-1.82(m,2H,CH 2 ),1.60-1.23(m,18H,5 x CH 3 and CH 2 and CH),1.03(d,J＝6.4Hz,3H,CH 3 ),0.97(t,J＝7.6Hz,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝198.8,169.8,166.1,155.7,146.9,131.0,129.7,126.5,120.6,99.2,80.7,75.1,69.6,66.0,42.5,34.3,32.5,29.9,28.0,26.1,19.4,18.7,16.5,11.2；IR(neat):v＝2966,2934,2877,1719,1683,1599,1463,1380,1368,1270,1201,1150,1104,1016cm -1 ；MS(ESI)m/z:489(M+H) + ；HRMS calcd m/z for C 28 H 41 O 7 [(M+H) + ]:489.2847,found:489.2840.
example 70
A reaction formula (70);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (3.1mg，0.005mmol)，NaOAc(3.3mg，0.04mmol)，Cu(OAc) 2 ·H 2 O (2.0 mg,0.01 mmol), 2y (89.5 mg,0.3 mmol), 1q (75.3 mg,0.2 mmol), THF (1 mL) were reacted for 24 hours to give E-3qy (90.0 mg,67%, purity 93%) (eluent: petroleum ether/diethyl ether/dichloromethane=2/1/1): a yellow liquid; [ alpha ] ] 30 D ＝+87.14(c＝0.625,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝10.14(d,J＝8.0Hz,1H,CHO),7.29(s,2H,Ar-H),7.27-7.15(m,5H,Ar-H),6.55(d,J＝7.6Hz,1H,＝CH),4.40(s,2H,CH 2 ),3.79(d,J＝15.2Hz,1H,one proton of SCH 2 ),3.17(d,J＝15.2Hz,1H,one proton of SCH 2 ),2.90(dd,J 1 ＝8.8Hz,J 2 ＝4.0Hz,2H,CH 2 ),2.59-2.46(m,2H,CH 2 ),2.46-2.36(m,2H,CH 2 ),2.29(m,1H,CH),2.21-1.90(m,7H),1.76-1.38(m,9H),1.14(s,3H,CH 3 ),0.96-0.83(m,6H,2 x CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝220.6,214.0,191.0,158.1,147.8,142.5,137.2,137.0,136.3,129.6,128.0,127.5,125.9,124.3,122.3,58.1,50.4,47.9,47.8,47.6,44.4,42.8,42.4,37.8,35.7,34.5,31.5,29.3,26.8,26.2,25.4,25.0,21.5,19.9,19.6,13.8；IR(neat):v＝2930,2864,1736,1659,1598,1501,1454,1371,1356,1257,1197,1173,1146,1053,1017,1007cm -1 ；MS(ESI)m/z:629(M+H) + ；HRMS calcd m/z for C 38 H 45 O 6 S[(M+H) + ]:629.2931,found:629.2924.
Example 71
A reaction formula (71);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (1.5mg，0.0025mmol)，NaOAc(1.6mg，0.02mmol)，Cu(OAc) 2 ·H 2 O (1.0 mg,0.005 mmol), 2y (44.8 mg,0.15 mmol), 1u (76.8 mg,0.1 mmol), THF (1 mL) was reacted for 24 hours to give E-3uy (32.6 mg, 32%) (crude profile monitoring showed 13% 1u remaining) (first column chromatography: eluent: dichloromethane, dichloromethane/ethyl acetate=50/1-40/1-30/1. Second column chromatography: petroleum ether, petroleum ether/ethyl ether/dichloromethane=2/1/1, to give 21.0mg pure product. Third column chromatography: petroleum ether, petroleum ether/ethyl ether/dichloromethane=2/1/1, to give 21.0mg pure product.): a pale yellow solid; melting point: 125.5-126.5 ℃ (failure to recrystallise, direct melting point of solid); [ alpha ]] 28 D ＝+48.67(c＝0.60,CHCl 3 )； 1 H NMR(400MHz,CDCl 3 ):δ＝7.88(s,1H,Ar-H),7.78-7.69(m,2H,Ar-H),7.64(dd,J 1 ＝8.4Hz,J 2 ＝1.6Hz,1H,Ar-H),7.59(s,1H,Ar-H),7.54(d,J＝2.4Hz,1H,Ar-H),7.47(dd,J 1 ＝8.4Hz,J 2 ＝1.6Hz,1H,Ar-H),7.34(dd,J 1 ＝8.4Hz,J 2 ＝1.2Hz,1H,Ar-H),7.32-7.27(m,1H,Ar-H),7.24-7.19(m,2H,Ar-H),6.96(d,J＝8.4Hz,1H,Ar-H),6.67(s,1H,＝CH),4.67-4.53(m,2H,CH 2 ),3.88(s,3H,OCH 3 ),3.68-3.56(m,1H,OCH),2.93-2.83(m,2H,CH 2 ),2.70-2.58(m,1H),2.57-2.44(m,2H),2.42-2.33(m,1H),2.31-2.22(m,1H),2.16(s,6H,3xCH 2 ),2.13-1.91(m,8H),1.91-0.81(m,47H),0.63(s,3H,CH 3 )； 13 C NMR(100MHz,CDCl 3 ):δ＝220.7,201.6,158.4,154.5,141.0,138.8,138.6,138.3,136.7,136.5,133.3,132.3,127.9,127.7,127.6,126.6,125.8,125.6,125.49,125.47,125.3,124.7,124.5,112.0,71.8,56.5,56.0,55.1,50.4,47.9,44.4,42.7,42.1,41.9,40.6,40.4,40.1,37.9,37.1,36.4,36.3,35.82,35.79,35.4,35.3,34.5,31.5,30.5,30.3,29.4,29.1,28.2,27.2,26.4,26.3,25.5,24.2,23.3,21.5,20.8,18.5,13.8,12.0；IR(neat):v＝3521,2926,2905,2852,1740,1681,1596,1495,1451,1374,1259,1236,1139,1067,1031,1010cm -1 ；MS(ESI)m/z:1019.7(M + )；HRMS calcd m/z for C 72 H 91 O 4 [(M+H) + ]:1019.6912,found:1019.6918.
Example 72
Equation (72);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (121.2 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.4mg,0.75 mmol), 1a (35.3 mg,0.5 mmol), methanol (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 77% nuclear magnetic yield.
Example 73
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A reaction formula (73);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (120.7 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.1mg,0.75 mmol), 1a (34.9 mg,0.5 mmol), 1, 4-dioxane (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 79% nuclear magnetic yield.
Example 74
A reaction formula (74);
into a dry reaction tubeSecondary addition of [ Cp. RhCl ] 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (120.6 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.3mg,0.75 mmol), 1a (35.1 mg,0.5 mmol), toluene (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 75% nuclear magnetic yield.
Example 75
A reaction formula (75);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (120.6 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.2mg,0.75 mmol), 1a (34.9 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 86% nuclear magnetic yield.
Example 76
A reaction formula (76);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (120.7 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.0mg,0.75 mmol), 1a (35.3 mg,0.5 mmol), acetonitrile (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel and washed with ethyl acetate (4X 5 mL)Washing and rotary steaming to remove the solvent, and obtaining the product E-3aa, wherein the nuclear magnetic yield is 81%.
Example 77
A reaction formula (77);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (121.2 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.2mg,0.75 mmol), 1a (35.1 mg,0.5 mmol), DCM (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL), and the solvent was removed by rotary evaporation to give the product E-3aa in a nuclear magnetic yield of 51%.
Example 78
A reaction formula (78);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (100.6 mg,0.5 mmol), 3-methoxyphenylboronic acid (2 a,116.7mg,0.75 mmol), 1a (35.0 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in a nuclear magnetic yield of 90%.
Example 79
A reaction formula (79);
to the drying directionSequentially adding [ Cp ] RhCl into the reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (20.4 mg,0.10 mmol), 3-methoxyphenylboronic acid (2 a,116.9mg,0.75 mmol), 1a (34.8 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in a nuclear magnetic yield of 85%.
Example 80
A reaction formula (80);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (5.0 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,116.4mg,0.75 mmol), 1a (35.2 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 86% nuclear magnetic yield.
Example 81
A reaction formula (81);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.7mg，0.0125mmol)，Cu(OAc) 2 ·H 2 O (5.1 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,117.7mg,0.75 mmol), 1a (35.2 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL), and the solvent was removed by rotary evaporation The product E-3aa is obtained, and the nuclear magnetic yield is 62%.
Example 82
A reaction formula (82);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(OAc) 2 ·H 2 O (120.8 mg,0.6 mmol), 3-methoxyphenylboronic acid (2 a,116.2mg,0.75 mmol), 1a (35.0 mg,0.5 mmol), methanol (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in a nuclear magnetic yield of 69%.
Example 83
Equation (83);
sequentially adding [ Cp ] RhCl to a dry reaction tube 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，CuSO 4 ·5H 2 O (6.2 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,116.3mg,0.75 mmol), 1a (35.1 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 92% nuclear magnetic yield.
Example 84
Equation (84);
sequentially adding into a dry reaction tubeIn [ Cp ] RhCl 2 ] 2 (7.9mg，0.0125mmol)，NaOAc(8.2mg，0.10mmol)，Cu(NO 3 ) 2 ·3H 2 O (6.0 mg,0.025 mmol), 3-methoxyphenylboronic acid (2 a,116.6mg,0.75 mmol), 1a (35.0 mg,0.5 mmol), THF (2.5 mL). The reaction tube was plugged with a rubber plug, and an air balloon was inserted to allow the reaction system to be in an air atmosphere and stirred at room temperature for 12 hours. The reaction mixture was filtered through a short column of silica gel, washed with ethyl acetate (4X 5 mL) and the solvent was removed by rotary evaporation to give the product E-3aa in 92% nuclear magnetic yield.
Example 85
A reaction formula (85);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (6.3mg，0.01mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.0 mg,0.05 mmol), 2-methoxyphenylboronic acid (2 aa,228.0mg,1.5 mmol), 1a (70.0 mg,1.0 mmol), THF (5 mL) were reacted for 24 hours to give E-3aaa with a nuclear magnetic resonance yield of 34%
Example 86
A reaction formula (86);
the procedure is as in example 1.[ Cp ] RhCl 2 ] 2 (15.8mg，0.025mmol)，NaOAc(16.4mg，0.20mmol)，Cu(OAc) 2 ·H 2 O (10.1 mg,0.05 mmol), 4-hydroxyphenylboronic acid (2 ab,211.1mg,1.5 mmol), 1a (70.1 mg,1.0 mmol), THF (5 mL) were reacted for 6 hours to give E-3aab with a nuclear magnetic resonance yield of 55%
The invention is not limited to the specific embodiments disclosed and described above. Some modifications and variations of the present invention should fall within the scope of protection of the appended claims without departing from the spirit and scope of the inventive concept. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (8)

1. A method for synthesizing 2-enal and/or 2-enone compound and deuterated or tritiated compound thereof in a stereospecific manner is characterized in that 2, 3-dienol reacts with organic boric acid in a first organic solvent under the action of rhodium catalyst, copper catalyst, alkali, air or oxygen to synthesize 2-enal and/or 2-enone compound and deuterated or tritiated compound thereof in a stereospecific manner; the reaction process is shown in the following reaction formula (a):
In the reaction scheme (a),
R 1 aryl, heterocyclyl, hydrocarbyl with functional groups;
R 2 hydrogen, deuterium, tritium, aryl, heterocyclyl, hydrocarbyl with functional groups;
R 3 hydrogen, deuterium, tritium, aryl, heterocyclyl, hydrocarbyl with functional groups;
H a hydrogen, deuterium, tritium;
H b hydrogen, deuterium, tritium;
wherein the R is 1 、R 2 、R 3 Wherein the aryl is phenyl with substituent groups at the ortho, meta and para positions, and the substituent groups are alkyl, alkenyl, phenyl, halogen, trifluoromethyl, alkoxy, alkoxycarbonyl, acyl, acyloxy, amido, sulfonyl, sulfonyloxy, hydroxyl, nitro, carboxyl, cyano and amino; the R is 1 、R 2 、R 3 The heterocyclic group in (a) refers to a 3-10 membered heterocyclic ring with a ring-forming atom being a carbon, nitrogen, oxygen or sulfur atom, and is an aliphatic ring, an aromatic ring or a ring formed by splicing two or more simple rings; the R is 1 、R 2 、R 3 In the hydrocarbon group with functional groups of acyl, hydroxy, halogen, alkoxy and alkoxycarbonylFormyl, acyloxy, amido, sulfonyl, sulfonyloxy, nitro, carboxyl, cyano;
the rhodium catalyst is any one or more of dichloro (pentamethyl cyclopentadienyl) rhodium (III) dimer, tris (triphenylphosphine) rhodium (I) chloride, bis (ethylene) rhodium (I) chloride dimer, (1, 5-cyclooctadiene) rhodium (I) chloride dimer, bis (ethylene) rhodium (I) acetylacetonate, (1, 5-cyclooctadiene) rhodium (I) chloride dimer, bis (norbornadiene) rhodium tetrafluoroborate (I), rhodium (II) acetate dimer, bis (hexafluoroantimonic acid) triacetonitrile (pentamethyl cyclopentadienyl) rhodium (III), rhodium (III) acetylacetonate, pentachloropenta-ammoniacal rhodium (III) dichloride, tris (ethylenediamine) rhodium (III) trichloride, potassium pentachlororhodium (III) acrylate, sodium hexachlororhodium (III) carboxylate, potassium hexachlororhodium (III) trichloride, rhodium (III) bromide, rhodium (III) iodide, rhodium (III) sulfate, rhodium (III) nitrate and potassium hexanitrorhodium (III) sulfate;
The copper catalyst is any one or more of copper acetate hydrate, copper acetate, copper sulfate hydrate, copper sulfate, copper nitrate hydrate, copper nitrate, copper chloride hydrate, copper chloride and copper bromide.
2. The method of claim 1, wherein,
R 1 aryl, heterocyclyl, C1-C40 hydrocarbyl bearing functional groups;
R 2 hydrogen, deuterium, tritium, aryl, heterocyclyl, C1-C40 hydrocarbyl bearing functional groups;
R 3 hydrogen, deuterium, tritium, aryl, heterocyclyl, C1-C40 hydrocarbyl bearing functional groups;
H a hydrogen, deuterium, tritium;
H b hydrogen, deuterium, tritium;
wherein the R is 1 、R 2 、R 3 Wherein the aryl is phenyl with substituent groups at the ortho, meta and para positions, and the substituent groups are C1-C40 alkyl, C2-C40 alkenyl, phenyl, halogen, trifluoromethyl, C1-C40 alkoxy, C1-C40 alkoxycarbonyl, acyl, acyloxy, amido, sulfonyl, sulfonyloxy, hydroxyl, nitro, trifluoromethyl, and the like,Carboxyl, cyano and amino; the R is 1 、R 2 、R 3 The heterocyclic group in (a) refers to a 3-10 membered heterocyclic ring with a ring-forming atom of carbon, nitrogen, oxygen or sulfur, and is an aliphatic ring, an aromatic ring or a ring formed by splicing two or more simple rings, and the heterocyclic group comprises thiophene, furan, pyrrole and pyridine; the R is 1 、R 2 、R 3 The functional group in the C1-C40 hydrocarbon group with functional group is acyl, hydroxyl, halogen, C1-C40 alkoxy, C1-C40 alkoxycarbonyl, acyl, acyloxy, amido, sulfonyl, sulfonyloxy, nitro, carboxyl and cyano.
3. The method according to claim 1, characterized in that it comprises in particular the following steps:
(1) Sequentially adding a rhodium catalyst, alkali, a copper catalyst, organic boric acid, 2, 3-dienol and a first organic solvent into a dried reaction tube, plugging the reaction tube with a rubber plug, inserting an air ball or an oxygen ball to enable the reaction tube to be in an air or oxygen atmosphere, and stirring for reaction at the temperature of-20-60 ℃;
wherein the first organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane, toluene, acetonitrile, methanol, ethanol, dichloromethane, diethyl ether, anisole, methyl tertiary butyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; the dosage of the first organic solvent is 1.0-20.0mL/mmol based on the dosage of the 2, 3-dienol shown in the reaction formula (a);
(2) After the reaction in the step (1) is completed, filtering the mixed solution in the reaction tube by using a short column of silica gel, washing the mixed solution by using a second organic solvent, concentrating the mixed solution, and performing rapid column chromatography to obtain the corresponding 2-enal or 2-enone compound and deuterated and tritiated compounds thereof;
Wherein the second organic solvent is one or more of ethyl acetate, diethyl ether, methanol, ethanol, dichloromethane, tetrahydrofuran, 1, 4-dioxane, acetone and acetonitrile; the second organic solvent is 1.0-200mL/mmol based on the amount of 2, 3-dienol shown in the reaction formula (a).
4. The method of claim 1, wherein the first organic solvent is any one or more of tetrahydrofuran, 1, 4-dioxane, toluene, acetonitrile, methanol, ethanol, methylene chloride, diethyl ether, anisole, methyl t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether.
5. The method of claim 1, wherein the base is any one or more of sodium acetate, sodium carbonate, sodium bicarbonate, potassium acetate, potassium carbonate, potassium bicarbonate, cesium carbonate, lithium carbonate, magnesium acetate, calcium acetate.
6. The method of claim 1, wherein the molar ratio of rhodium catalyst, copper catalyst, base, organoboronic acid, 2, 3-dienol is (0.005-0.10): (0.005-1.20): (0-0.60): (1.0-3.0): 1.0; and/or the temperature of the reaction is-20-60 ℃.
7. Use of the method as recited in any one of claims 1-5 in the synthesis of deuterated 2-enal, deuterated 2-enone.
8. Use of the method according to any one of claims 1-5 for the structural modification of a drug molecule, a natural product molecule.
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