CN116120193A - Novel method for synthesizing chiral triphenylmethane compounds - Google Patents
Novel method for synthesizing chiral triphenylmethane compounds Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
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- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Abstract
The invention discloses a novel method for synthesizing chiral triphenylmethane compounds, which is to realize direct alkylation reaction of para-position of aniline in a reaction solvent by taking chiral phosphoric acid as a catalyst and o-hydroxybenzyl alcohol and diphenylamine as reaction raw materials, and obtain the chiral triphenylmethane compounds with high enantioselectivity. The method has the advantages of high regioselectivity and stereospecificity, mild reaction conditions, simple reaction operation, low energy consumption, environmental friendliness and good yield.
Description
Technical Field
The invention relates to synthesis of chiral triphenylmethane compounds, in particular to a method for synthesizing chiral triphenylmethane compounds with high enantioselectivity by using an organic catalytic system, and belongs to the technical field of organic compound process application.
Background
Triarylmethane derivatives are important structural modules in pharmaceutical chemistry, material science and organic synthesis, and are widely existing in natural products and drug molecules, and can be used as anti-tumor, anti-inflammatory, anti-tuberculosis and antihypertensive drugs. Because of the lack of sufficient spatial diversity between aromatic rings, catalyzing asymmetric synthesis of such molecules is a long-standing challenge in organic synthesis, and chiral synthesis of such compounds has been receiving widespread attention from chemical and pharmaceutical scientists. The current methods for synthesizing triarylmethane are as follows: (1) metal-catalyzed activation of C-H bonds; (2) a metal catalyzed cross-coupling reaction; (3) Friedel-crafts alkylation. Most of the reaction processes are complex and have harsh conditions, and under mild conditions, a synthetic method for synthesizing chiral triphenylmethane through organocatalytic aniline para-C-H alkylation reaction is not reported yet.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a novel method for synthesizing chiral triphenylmethane compounds, solves the problems of complex reaction process and severe conditions in most of the prior art, and provides a novel method for synthesizing chiral triphenylmethane derivatives through the para-C-H alkylation of aniline by organic catalysis, which has the advantages of mild reaction conditions, low cost and high enantioselectivity.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: the new method for synthesizing chiral triphenylmethane compounds uses compounds 1 and 2 as reaction raw materials, chiral phosphoric acid as a catalyst, and chiral triphenylmethane compound 3 can be obtained by reaction under the condition of reaction solvent and additive at room temperature (25 ℃); the reaction process is shown in the following formula:
wherein R1, R2, R3 and R4 are alkyl, aryl, halogen, nitro, hydroxyl, methoxy, acetyl and diazo.
Preferably, the catalyst is used in an amount of 10% of the total mass of the reactants.
Preferably, the reaction solvent is one of toluene, fluorobenzene, benzotrifluoride, methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, diethyl ether, methylcyclopentyl ether, acetonitrile and xylene compounds.
Preferably, the chiral phosphoric acid catalyst is selected from one of binaphthyl skeleton derivatives, octahydrobinaphthyl skeleton derivatives and spiroindene ring skeleton derivatives; the structural formula of the binaphthyl skeleton derivative is
Wherein G is selected from one of 2-naphthyl, 2,4, 6-triisopropylphenyl, 9-anthryl, 9-phenanthryl, 2,4, 6-trimethylphenyl and 3, 5-bis (trifluoromethyl) phenyl; the structural formula of the octahydrobinaphthyl skeleton derivative is +.>
Wherein G is selected from one of 1-naphthyl, 3, 5-di (trifluoromethyl) phenyl, 2,4, 6-triisopropylphenyl and 2,4, 6-trimethylphenyl; the structural formula of the spiroindene ring skeleton derivative is
G is selected from one of 1-naphthyl, 3, 5-di (trifluoromethyl) phenyl, 2,4, 6-triisopropylphenyl and 2,4, 6-trimethylphenyl.
Preferably, the chiral phosphoric acid catalyst has the structural formula of
Wherein G is selected from 2,4, 6-trimethylphenyl.
Preferably, the reaction additive is sodium sulfate, magnesium sulfate,
Molecular sieves, & gt>
Molecular sieves, & gt>
One of the molecular sieves.
Preferably, the molar mass ratio of compound 1 to compound 2 is 1:1.2.
Preferably, the specific reaction process is shown in the following reaction formula:
in a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction is finished, column chromatography purification is directly carried out, and 3a can be obtained.
Preferably, the column chromatography is silica gel column chromatography, and the eluting machine adopts petroleum ether/ethyl acetate mixed solution with the volume ratio of 5:1.
(III) beneficial effects
The invention provides a novel method for synthesizing chiral triphenylmethane compounds. The beneficial effects are as follows: compared with the prior art, the invention adopts chiral phosphoric acid as a catalyst in the process of synthesizing the chiral triphenylmethane derivative by a one-step method, so that the enantioselectivity of the reaction is well controlled; the reaction conditions are conventional conditions, so that the mild reaction conditions are realized, the method is more suitable for industrial mass production, and the application range of the method is widened; and a plurality of substrates are adopted as reactants, so that products with structural diversity and complexity are obtained, and the enantioselectivity is high.
Detailed Description
In the examples below, unless otherwise indicated, the experimental methods described are generally carried out under conventional conditions or conditions recommended by the manufacturer; the raw materials and reagents shown are all commercially available.
The synthetic route of chiral triphenylmethane derivatives is as follows:
the catalysts selected in the following test examples were all
Wherein G is selected from 2,4, 6-trimethylphenyl.
The present invention will be described in further detail with reference to the following specific examples, to which the present invention is not limited. 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 data presented in the examples below include specific operations and reaction conditions and products. The purity of the product was identified by nuclear magnetic resonance.
Example 1
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3a (80%). 95% ee,1H-NMR (400 mhz, cdcl 3): δ (ppm): 7.26 (t, 2H, j=0.8 hz,1.2 hz), 7.25-7.22 (M, 3H), 7.13 (dd, 3H, j=7.6 hz,2.0 hz), 7.06-6.99 (M, 6H), 6.92-6.87 (M, 1H), 6.86-6.79 (M, 1H), 5.68 (s, 1H), 5.65 (s, 1H), 4.76 (s, 1H): 13C-NMR (100 mhz, cdcl 3): δ (ppm 153.51, 143.01, 142.80, 141.85, 134.68, 130.58, 130.43, 130.24, 129.35, 128.58, 127.92, 126.66, 121.02, 120.78, 117.85, 4, 50.36.hrms (esicad.for C25H22 no+m, 463+3h), 4.37 n=3.37 n=20/min, and (95×39.8 min, 39-39H).
Example 2
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1b,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3b (68%). 91% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm) 7.31 (t, 2H, j=7.2 Hz,7.8 Hz), 7, 24 (q, 3H, j=7.8 Hz,7.8 Hz), 7.15 (d, 2H, j=7.2 Hz), 7.06 (d, 2H, j=7.8 Hz), 7.15 (q, 4H, j=8.4 Hz,9.0 Hz), 6.95-6.90 (M, 2H), 6.71 (d, 1H, j=8.4 Hz), 6.64 (s, 1H), 5.68 (s, 1H), 5.61 (s, 1H), 4.53 (s, 1H), 2.19 (s, 3H) 13C-NMR (150 mhz, cdcl 3): delta (ppm) 151.28, 143.05, 142.85, 141.78, 134.76, 130.88, 130.26, 130.23, 129.94, 129.35, 129.33, 128.57, 25.62, 67, 62, 67, and (v=37H), and lambda (v=20, 37H), 6.64 (s, 1H), 5.61 (s, 1H), 4.53 (s, 1H), 2.19 (s, 3H), 2.19 (s, 37C-NMR (150, 3H), and 3d, 62, 37M (n) 4, 37H).
Example 3
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1c,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3c (65%). 93% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.30 (t, 2H, j=7.2 Hz,7.8 Hz), 7.26-7.22 (M, 3H), 7.16 (d, 2H, j=7.8 Hz), 7.06-6.99 (M, 6H), 6.91 (t, 1H, j=7.2 Hz,7.2 Hz), 6.75 (d, 1H, j=8.4 Hz), 6.67 (dd, 1H, j=3.0 Hz,3.0 Hz), 6.41 (d, 1H, j=3.0 Hz), 5.68 (s, br, 1H), 5.61 (s, 1H), 4.40 (s, br, 1H), 3.65 (s, 3H) 13C-NMR (150 mhz, cdcl 3): delta (ppm): 153.69, 147.48, 143.01, 142.53, 141.88, 134.43, 132.04, 130.22, 129.35, 129.30, 128.62, 126.73, 121.02, 117.86, 117.83, 116.89, 116.80, 112.01, 55.58, 50.60.Hrms (ESI): calcd.for C26H24NO2[ m+h ] +:382.1802,found:382.1803.HPLC analysis:Daicel CHIRALCEL AD-3, n-hexane/i-prah=80/20, flow rate=1.0 mL/min, λ= 254nm,retention time:tR =27.34 min (minor), tr=47.69 min (major).
Example 4
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1d,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain a white solid 3d (85%). 91% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.32 (t, 2H, J=7.2 Hz,7.8 Hz), 7.27-7.24 (M, 4H), 7.14 (d, 2H, J=7.2 Hz), 7.07 (dd, 2H, J=1.2 Hz,1.2 Hz), 7.02-6.99 (M, 4H), 6.94-6.91 (M, 2H), 6.70 (d, 1H, J=8.4 Hz), 5.70 (s, 1H), 5.57 (s, 1H), 4.75 (s, 1H): 13C-NMR (150 MHz, CDCl 3): delta (ppm): 152.70, 142.80, 142.20, 141.86, 133.54, 132.97, 3995, 130.16, 129.38, 129.22, 128.78, 4, 121.24, 118.07, 118.05, 117.74, 113.14, 113.40.40.94-6.91 (M, 2H), 6.70 (d, 1H), 5.70 (s, 1H), 4.75 (s, 1H), 13C-NMR (150 MHz, CDCl 3): delta (ppm) and (3) of Pr, 39.75 (3H, 37H) =3.75 (3H) =7.7.7H).
Example 5
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1e,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3e (68%). 96% ee,1H-NMR (400 mhz, cdcl 3): δ (ppm): 7.31 (t, 2H, j=7.2 Hz,7.6 Hz), 7.27-7.23 (M, 3H), 7.12 (d, 2H, j=7.6 Hz), 7.05 (d, 2H, j=8.4 Hz), 6.99 (t, 6H, j=9.2 Hz,10.4 Hz), 6.92 (t, 1H, j=7.6 Hz,7.2 Hz), 6.68 (d, 1H, j=8.8 Hz), 5.70 (s, 1H), 5.57 (s, 1H), 5.10 (s, 1H): 13C-NMR (100 mhz, cdcl 3): δ (ppm): 154.31, 142.86, 142.21, 142.05, 133.92, 131.70, 130.17, 129.94, 129.38, 129.25, 3869, 123.80, 120.74, 37.97, and (39.38), and (39.38, 37H, 37.8.8 Hz), 5.70 (s, 1H), 5.57 (s, 1H), 5.10 (s, 1H): 13C-NMR (100 mhz, cdcl 3): δ (3) δ (ppm, 154.31, 37.39, 37, 37.38, 37H).
Example 6
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1f,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3f (65%). 94% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.31 (t, 2H, j=7.8 Hz,7.2 Hz), 7.26-7.23 (M, 3H), 7.14 (d, 2H, j=7.2 Hz), 7.06 (d, 2H, j=7.8 Hz), 7.00 (s, 4H), 6.92 (t, 1H, j=7.8 Hz,7.2 Hz), 6.75 (q, 1H, j=6.6 Hz,6.6 Hz), 6.57-6.55 (M, 2H), 5.69 (s, 1H), 5.55 (s, 1H), 4.96 (s, br, 1H) 13C-NMR (150 mhz, cdcl 3): delta (ppm): 163.13, 161.51, 154.51 (d, j=12 Hz), 142.88, 142.43, 142.08, 134.14, 131.22 (d, j=9 Hz), 130.16, 129.38, 129.24, 128.70, 126.85, 126.41 (d, j=3 Hz), 121.18, 117.89 (d, j=31.5 Hz), 107.35 (d, j=19.5 Hz), 103.87 (d, j=25.5 Hz), 50.01.19FNMR (560 mhz, cdcl 3): delta (ppm): 114.72.hrms (ESI): calcd.for C25H21FNO [ m+h ] +:370.1602,found:370.1601.HPLC analysis:Daicel CHIRALCEL AD-3, n-hexane/i-proh=80/20, flow rate=1.0 mL/min, lambda= 254nm,retention time:tR =12.91 min (minor), tr=15.07 min (major).
Example 7
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1g,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3g (71%) of a white solid. 92% ee,1H-NMR (600 mhz, cdcl 3): δ (ppm): 7.17 (t, 2H, j=7.2 Hz,9.0 Hz), 7.07-7.03 (M, 3H), 6.99 (d, 2H, j=8.4 Hz), 6.97 (d, 2H, j=7.8 Hz), 6.94 (s, 4H), 6.84 (t, 1H, j=7.2 Hz,7.8 Hz), 6.79-6.73 (M, 3H), 5.53 (s, 1H), 4.72 (s, br, 1H): δ (ppm): 153.54, 142.86, 141.51, 3995, 136.29, 130.66, 130.36, 130.22, 129.37, 3995, 121.24, 120.72, 118.07, 117.96, 116.18, 50.03, 21.08 (escai): 7.26.2 Hz,7.8 Hz), 6.79-6.73 (M, 3H), 5.53 (s, 1H), 4.72 (s, br, 1H): 13C-NMR (150 mhz, cdcl 3): δ (ppm): 153.54, 3997, 3999, 3995, 3839, 3834, 379, 3834, 3795, 3272, hr72, 50.03, 21.03, 21.08 (7.08, ESc (d) =7.08) and (d=1H).
Example 8
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol substrate 1h,0.12mmol substrate 2a,0.01mmol CPA and 100mg anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain a white solid (74%) for 3 h. 93% ee,1H-NMR (600 mhz, cdcl 3): δ (ppm): 7.27-7.23 (M, 4H), 7.14 (t, 1H, j=7.8 hz,7.2 hz), 7.06 (q, 4H, j=8.4 hz,8.4 hz), 8.00-6.97 (M, 4H), 6.91 (t, 1H, j=7.2 hz,7.8 hz), 6.86 (t, 1H, j=7.2 hz,7.8 hz), 6.79 (t, 1H, j=10.2 hz,8.4 hz), 5.75 (s, br, 1H), 5.65 (s, 1H), 4.75 (s, 1H): 13C-NMR (150 mhz, cdcl3 δ (ppm): 153.32. 142.92, 141.99, 49, 134.29, 132.32, 130.69, 130.33, 130.19, 4, 46356, 4639, 35, 95 j=7.48 hz), 6.86 (t, 37H, 463, 39.35, 39.25, 39.48H), 95 (g., 39.48H), 37H, 39.48H, 39 (n=35, 37H), 37H, 39.48H), 37 (n) and (n) of the fluid (n=35, 37.48H, 37M, 48H).
Example 9
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1i,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3i (77%). 90% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.25-7.22 (m, 2H), 7.20-7.18 (m, 2H), 7.13 (td, 1H, J=7.8 Hz,6.0 Hz), 7.07-7.04 (m, 4H), 7.01-6.98 (m, 4H), 6.91 (t, 1H, J=7.2 Hz,7.2 Hz), 6.87-6.82 (m, 2H), 6.80 (dd, 1H, J=7.8 Hz,7.8 Hz), 5.71 (s, br, 1H), 5.61 (s, 1H), 4.75 (s, br, 1H), 2.45 (s, 3H) 13C-NMR (150 MHz, CDCl 3):
δ(ppm):153.44，143.00，141.87，139.81，136.50，134.58，130.44，130.37，130.19，129.82，129.36，127.96，126.82，121.05，120.81，117.85，117.83，116.14，49.75，15.92.HRMS(ESI):calcd.for C26H24NOS[M+H]+:398.1573，found:398.1577.HPLC analysis:Daicel CHIRALCEL AD-3，n-hexane/i-PrOH＝80/20，flow rate＝1.0mL/min，λ＝254nm，retention time:tR＝31.19min(major)，tR＝39.53min(minor)。
example 10
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1j,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3j (78%). 93% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.25-7.23 (M, 2H), 7.19 (t, 1H, j=7.2 Hz,7.8 Hz), 7.14 (td, 1H, j=7.8 Hz,6.0 Hz), 7.05 (dd, 3H, j=8.4 Hz,7,8 Hz), 7.03-6.99 (M, 5H), 6.94 (d, 1H, j=7.8 Hz), 6.92-6.89 (M, 1H), 6.86-6.82 (M, 2H), 6.81 (dd, 1H, j=7.8 Hz,7.8 Hz), 5.67 (s, 1H), 5.59 (s, 1H), 4.75 (s, 1H), 2.30 (s, 3H) 13C-NMR (150 mhz, cdcl 3): delta (ppm): 153.54, 143.06, 142.61, 141.79, 138.25, 134.73, 130.64, 130.43, 130.24, 130.06, 129.35, 128.49, 127.89, 127.53, 126.36, 121.00, 120.75, 117.85, 117.81, 116.20, 50.42, 21.54.Hrms (ESI): calcd.for C26H24NO [ m+h ] +:366.1852,found:366.1849.HPLC analysis:Daicel CHIRALCEL IA,n-hexane/i-proh=75/25, flow rate=1.0 mL/min, λ= 254nm,retention time:tR =11.06 min (minor), tr=13.41 min (major).
Example 11
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1k,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3k (78%) as a white solid. 92% ee,1H-NMR (600 mhz, cdcl 3): δ (ppm): 7.25-7.22 (M, 3H), 7.15-7.13 (M, 1H), 7.06-6.99 (M, 6H), 6.91 (t, 1 h.j=7.8 Hz,7.2 Hz), 6.87-6.84 (M, 2H), 6.79 (td, 2H, j=7.8 Hz,5.4 Hz), 6.75 (d, 1H, j=7.8 Hz), 6.71 (d, 1H, j=2.4 Hz), 5.68 (s, 1H), 5.61 (s, 1H), 4.73 (s, 1H), 3.74 (s, 1H): 13C-NMR (150 mhz, cdcl 3): δ (ppm): 159.80, 153.50, 144.44, 143.03, 141.85, 134.48, 130.42, 130.38, 130.21, 144.44, 127, 53, 5634, 56, 5295.4 Hz), 6.75 (d, 52H), 6.71 (d, 1H), 5.71 (d, 1H), j=2.73 (j=2.4 Hz), 5.68 (s, 1H), 4, 5.73 (s, 1H), 4, 1H), 4.73 (s, 37, 1H), 4).
Example 12
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1l,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3l (76%) of a white solid. 95% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.26-7.21 (M, 4H), 7.14 (td, 2h.j=7.8 hz,7.8 hz), 7.04-7.00 (M, 5H), 6.92 (t, 1H, j=7.2 hz,7.2 hz), 6.87 (td, 1H, j=7.8 hz,7.2 hz), 6.82 (dd, 1H, j=7.8 hz,7.2 hz), 6.79 (dd, 1H, j=7.8 hz,7.8 hz), 5.69 (s, 1H), 5.65 (s, 1H), 4.71 (s, 1H). 13C-NMR (150 mhz, cdcl 3): δ (ppm): 153.27, 145.30, 142.90, 142.04, 134.39, 134.02, 130.37, 130.20, 129.97, 129.67, 129.42, 129.37, 128.09, 127.57, 126.76, 121.16, 120.93, 117.99, 117.75, 116.06, 49.75.Hrms (ESI): calcd.for C25H21ClNO [ m+h ] +:386.1306,found:386.1304.HPLC analysis:Daicel CHIRALCEL IA,n-hexane/i-prah=80/20, flow rate=1.0 mL/min, λ= 254nm,retention time:tR =13.18 min (minor), tr=15.59 min (major).
Example 13
In a 10mL reaction tube, 1.0mL of toluene was added, 0.1mmol of substrate 1m,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3m (76%) as a white solid. 95% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm) 7.25-7.23 (M, 2H), 7.19-7.10 (M, 4H), 7.05 (d, 2H, j=7.8 Hz), 7.01-6.97 (M, 4H), 6.92-6.87 (M, 2H), 6.84 (td, 1H, j=7.8 Hz,7.2 Hz), 6.80 (d, 1H, j=7.8 Hz), 7.50 (dd, 1H, j=7.8 Hz,7.8 Hz), 5.73 (s, 1H), 5.67 (s, 1H), 4.67 (s, 1H), 2.23 (s, 3H) 13C-NMR (150 mhz, cdcl3): delta (ppm) 153.49, 143.08, 141.75, 141.13, 136.87, 134.10, 130.65, 130.26, 130.22, 129.35, 128.87, 127.84, 5286, 134.10, 120.98, 120.85, 5653, 5662, and (72, 52H), and 72, thereby allowing for a range of positive and a range of v=75 to be expressed by a total of v=3/min/v=3, 3H, and a range of v=3.35, 3C-v/v, 3H, 3C-v (150M, 3H).
Example 14
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1n,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3n (69%) as a white solid. 95% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm) 7.25-7.21 (M, 4H), 7.15 (td, 2H, j=7.2 hz,7.8 hz), 7.07-7.05 (M, 2H), 7.04-6.99 (M, 5H), 6.93-6.91 (M, 1H), 6.87 (td, 1H, j=7.8 hz,7.2 hz), 6.82 (dd, 1H, j=7.2 hz,7.8 hz), 6, 80 (dd, 1H, j=8.4 hz,7.8 hz), 5.69 (s, 1H), 5.66 (s, 1H), 4.69 (s, 1H) 13C-NMR (150 mhz, cdcl3): delta (ppm) 153.27, 145.29, 142.89, 142.04, 134.39, 134.01, 130.37, 130.19, 129.96, 129.66, 129.42, 129.37, 128.08, 127.56, 53, 57, 62, and 72, and (72, 52 h=8.48 hz), 5.69 (s, 1H), 5.66 (s, 1H), 4.69 (s, 1H), 13C-NMR (150 mhz, cdcl3):, 37 ppm (37, 37 mL), and 3 (n=37, 37, 48H).
Example 15
In a 10mL reaction tube, 1.0mL of toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2b,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3o (88%) as a white solid. 95% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm) 7.20 (t, 2H, j=7.8 Hz,7.2 Hz), 7.13 (t, 2H, j=7.2 Hz,7.2 Hz), 7.04 (q, 3H, j=7.8 Hz,7.8 Hz), 6.97 (d, 2H, j=7.8 Hz), 6.89 (q, 4H, j=8.4 Hz,7.8 Hz), 6.84 (d, 2H, j=8.4 Hz), 6.77-6.72 (M, 2H), 6.71 (d, 1H, j=7, 8 Hz), 5.53 (s, 1H), 5.48 (s, 1H), 4.62 (s, 1H) 13C-NMR (150 mhz, cdcl 3): delta (ppm 153.53, 142.83, 142.70, 140.20, 133.84, 49, 130.64, 130.44, 130.22, 129.88, 129.35, 128.58, 4634, 4639, 4639.35, 4639, 39.75 (d, 39.39, 39.75H), and 39.39-95 (d, 39H, 39 h=39, 39-39H, 39H) v (v=39, 39-39H, 39H).
Example 16
In a 10mL reaction tube, 1.0mL of toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2c,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3p (92%) as a white solid. 95% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.29 (t, 2H, j=7.2 Hz,7.8 Hz), 7.22 (q, 4H, j=3.0 Hz,7.2 Hz), 7.15-7.11 (M, 3H), 7.04 (dd, 2H, j=3.0 Hz,4.2 Hz), 6.97 (d, 2H, j=8.4 Hz), 6.85-6.81 (M, 6H), 6.79 (d, 1H, j=8.4 Hz), 5.61 (s, 1H), 5.46 (s, br, 1H), 4.80 (s, 1H), 3.77 (s, 3H). 13C-NMR (150 mhz, cdcl3): δ (ppm): 155.25, 153.56, 143.91, 142.92, 135.70, 133.12, 3999, 129.35, 128.55, 127.88, 84, 122.15, 120.74, 116.20, 130.22, 48, 52.34, 58, and (d=26, 1H), 4.80 (s, 1H), 3.77 (s, 3H): 13C-NMR (150 mhz, cdcl3) 3, 37C-NMR (150 mL, 37H).
Example 17
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of the substrate 1a,0.12mmol of the substrate 2d,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3q (97%) as a white solid. 94% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.54 (d, 2H, j=8.4 Hz), 7.48 (d, 2H, j=8.4 Hz), 7.39 (t, 2H, j=7.2 Hz,7.8 Hz), 7.26-7.21 (M, 3H), 7.16-7.12 (M, 3H), 7.10 (d, 2H, j=8.4 Hz), 7.03 (q, 4H, j=9.6 Hz,6.6 Hz), 6.87-6.83 (M, 2H), 6.79 (d, 1H, j=7.8 Hz), 5.73 (s, 1H), 5.66 (s, 1H), 4.75 (s, 1H), 13C-NMR (150 mhz, cdcl 3): δ (ppm): 153.51, 142.82, 142.49, 141.55, 140.86, 134.99, 133.75, 130.48, 130.32, 129.38, 128.79, 128.62, 5200, 128, 62, 7458, 126.64, 37 h=37H), and 72, 52.37 (n=37H), 6.37-37H, 37C-37 mg (n=37, 37H).
Example 18
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2e,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3r (88%) as a white solid. 92% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.21 (t, 2H, j=7.8 Hz,7.2 Hz), 7.14 (t, 2H, j=7.2 Hz,7.2 Hz), 7.08 (d, 2H, j=9.0 Hz), 7.04 (dd, 3H, j=7.2 Hz,7.2 Hz), 6.94 (d, 2H, j=8.4 Hz), 6.86 (q, 4H,7.2 Hz), 6.77-6.72 (M, 2H), 6.70 (d, 1H, j=7.8 Hz), 5.56 (s, 1H), 5.54 (s, 1H), 4.61 (s, 1H) 13C-NMR (150 mhz, cdcl 3): δ (ppm) 153.44, 142.72, 141.77, 141.31, 135.33, 130.49, 130.43, 130.35, 129.33, 129.28, 3860, 127.96, 125.49, and (d, 37.29, 37.8, and (d=7.8 Hz), 5.56 (s, 1H), 4.61 (s, 1H): 13C-NMR (150 mL ), and 37.37 mg, 37.38, 37 mL (d=37.29, 37.25).
Example 19
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of the substrate 1a,0.12mmol of the substrate 2f,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain a white solid 3s (93%). 94% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.30 (t, 4H, J=8.4 Hz,7.2 Hz), 7.23 (t, 1H, J=7.8 Hz,6.6 Hz), 7.14 (t, 3H, J=7.8 Hz,7.2 Hz), 7.03 (d, 2H, J=7.8 Hz), 6.97 (d, 2H, J=8.4 Hz), 6.90 (d, 2H, J=8.4 Hz), 6.87-6.82 (m, 2H), 6.80 (d, 1H, J=7.8 Hz), 5.66 (s, 1H), 5.64 (s, 1H), 4.73 (s, 1H) & 13C-NMR (150 MHz, CDCl 3):
δ(ppm):153.44，142.72，142.32，141.09，135.51，132.19，130.48，130.44，130.36，129.33，128.61，127.97，126.71，120.83，119.03，118.30，116.15，112.62，50.28.HRMS(ESI):calcd.for C25H21BrNO[M+H]+:430.0801，found:430.0800.HPLC analysis:Daicel CHIRALCEL IA，n-hexane/i-PrOH＝75/25，flow rate＝1.0mL/min，λ＝254nm，retention time:tR＝10.05min(minor)，tR＝11.97min(major)。
example 20
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2g,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3t (78%) of a white solid. 82% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 8.12 (d, 2H, j=9.0 Hz), 7.33 (t, 2H, j=7.8 Hz,7.2 Hz), 7.26 (s, 2H), 7.17 (q, 6H, j=7.8 Hz,7.2 Hz), 6.94 (d, 2H, j=9.0 Hz), 6.88 (t, 1H, j=7.2 Hz,7.8 Hz), 6.84-6.81 (M, 2H), 6.24 (s, 1H), 5.76 (s, 1H), 4.71 (s, 1H). 13C-NMR (150 mhz, cdcl 3): δ (ppm 153.31, 150.03, 142.45, 139.82, 139.13, 137.96, 130.64, 3995, 130.14, 129.31, 128.65, 128.06, 126.81, 126.24, 121.82, 120.89, 116.05, 113.72, 50.16.16.hrc (ESI) for c.25M, 1H), 4.71 (s, 1H), 4.13C-NMR (150 ppm, cdcl 3): δ (ppm 153.31, 150.03, 142.45, 139.82, 139.13, 137.96, 130.64, 3839, 39, 39.94, and 3.12.1 mL).
Example 21
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of the substrate 1a,0.12mmol of the substrate 2h,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3u (92%) as a white solid. 94% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm) 7.29 (t, 2H, j=7.2 Hz,7.2 Hz), 7.22 (d, 1H, j=9.0 Hz), 7.13 (q, 3H,6.6Hz,6.0 Hz), 6.97 (d, 4H, j=8.4 Hz), 6.85-6.79 (M, 5H), 6.73 (d, 2H, j=7.8 Hz), 5.61 (s, 1H), 5.44 (s, br, 1H), 5.00 (s, br, 1H), 4.90 (s, 1H). 13C-NMR (150 mhz, cdcl 3): delta (ppm): 153.50, 151.06, 143.90, 3995, 135.74, 133.18, 130.72, 130.44, 130.23, 129.35, 3996, 4639, 126.61, 122.39, 120.78, 116.21, 116.14, 115.82, 50.32.32.32.cald (ESI) for c.86/d (86, 37 h=25M, 48H), and 48+75/min (prjh) for 25+25/min.
Example 22
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of the substrate 1a,0.12mmol of the substrate 2i,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3v (62%) as a white solid. 82% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.77-7.75 (M, 4H), 7.39 (t, 2H, j=7.2 hz,7.8 hz), 7.31 (t, 1 h.j=7.2 hz,7.2 hz), 7.23 (t, 2H, j=7.2 hz,7.8 hz), 7.16 (t, 2H, j=9.6 hz,5.4 hz), 7.07 (q, 3H, j=4.2 hz,5.4 hz), 7.04 (s, 1H), 7.03-6.99 (M, 4H), 6.79-6.71 (M, 3H), 5.93 (s, 1H), 5.62 (s, 1H), 4.64 (s, 1H) 13C-NMR (150 mhz, cdcl 3): δ (ppm): 153.42, 152.97, 146.53, 146.40, 142.63, 139.84, 136.79, 130.44, 130.42, 130.39, 130.03, 129.33, 129.01, 128.62, 127.99, 126.73, 124.93, 122.45, 120.84, 119.88, 116.12, 115.79, 50.28.Hrms (ESI): calcd.for C31H26N3O [ m+h ] +:456.2070,found:456.2067.HPLC analysis:Daicel CHIRALCEL IA,n-hexane/i-proh=75/25, flow rate=1.0 mL/min, λ= 254nm,retention time:tR =10.26 min (minor), tr=11.26 min (major).
Example 23
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2j,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3w (81%) of a white solid. 93% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.85 (d, 2H, j=7.8 Hz), 7.32 (t, 2H, j=7.8 Hz,7.2 Hz), 7.25 (s, 1H), 7.15 (t, 3H, j=7.8 Hz,9.0 Hz), 7.10 (s, 4H), 6.97 (d, 2H, j=7.8 Hz), 6.88-6.82 (M, 3H), 6.08 (s, 1H), 5.75 (s, 1H), 5.05 (s, br, 1H), 2.51 (s, 3H). 13C-NMR (150 mhz, cdcl3): δ (ppm 196.62, 153.49, 148.36, 142.71, 139.06, 137.72, 130.68, 130.44, 130.42, 130.35, 129.34, 128.94, 128.58, 127.96, 126.69, 120.73, 120.66, 116.05, 114.41, 50.14, 26.15.i (escad=2H), 2.51 (s, 3H): δ (ppm 196.62, 148.36, 142.71, 139.06, 137.72, 39329, 4639, 5229, 5252.14, 52.14, 26.15.i) (=2H), and (hc=2H) =2.37H).
Example 24
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2k,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain 3X (89%) as a white solid. 86% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.20 (t, 2H, j=7.8 Hz,7.2 Hz), 7.14 (d, 2H, j=7.2 Hz), 7.04 (dd, 4H, j=8.4 Hz,7.8 Hz), 6.91 (s, 1H), 6.88 (d, 2H, j=8.4 Hz), 6.84 (d, 1H, j=7.8 Hz), 6.75-6.70 (M, 5H), 5.51 (s, 1H), 5.17 (s, 1H), 4.65 (s, 1H), 2.18 (s, 3H), 2.10 (s, 3H). 13C-NMR (150, cdcl 3): δ (ppm): 153.57, 143.60, 142.88, 138.27, 133.17, 132.13, 131.69, 130.70, 39356, 130.17, 384, 129.36, 128.57, 29, 127.26, 126.63, 120.95, 4630.84, 120.88, and (s, 48, 95), 4.18 (s, 48, 120H), 2.18 (s, 3H), 2.10 (s, 3H), 13C-NMR (150 mhz), and (d, 37 m=37, 37).
Example 25
In a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2l,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction was completed, column chromatography purification was directly performed to obtain white solid 3y (96%). 98% ee,1H-NMR (600 MHz, CDCl 3): delta (ppm): 7.27 (t, 2H, j=7.2 Hz,7.2 Hz), 7.22 (t, 1H, j=6.6 Hz,7.2 Hz), 7.15 (d, 2H, j=7.2 Hz), 7.11 (q, 1H, j=6.6 Hz,6.6 Hz), 7.06 (d, 2H, j=7.8 Hz), 6.83 (dd, 5H, j=7.2 Hz,6.6 Hz), 6.74 (d, 1H, j=7.8 Hz), 6.46 (s, 1H), 6.42 (d, 1H, j=8.4 Hz), 5.89 (s, 1H), 5.49 (s, br, 1H), 5.14 (s, br, 1H), 3.77 (s, 3H), 3.64 (s, 3H) 13C-NMR (150 mhz, cdcl 3). Delta (ppm): 157.81, 155.40, 153.77, 145.54, 142.59, 135.49, 130.85, 130.57, 130.03, 129.30, 128.34, 127.64, 126.36, 122.49, 121.31, 120.53, 116.15, 114.71, 107.71, 99.00, 55.66, 55.60, 43.32.Hrms (ESI): calcd.for C27H26NO3[ m+h ] +:412.1907,found:412.1906.HPLC analysis:Daicel CHIRALCEL IA,n-hexane/i-proh=75/25, flow rate=1.0 mL/min, λ= 254nm,retention time:tR =21.26 min (major), tr=24.20 min (minor).
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A novel method for synthesizing chiral triphenylmethane compounds is characterized in that the chiral triphenylmethane compounds 3 can be obtained by taking the compounds 1 and 2 as reaction raw materials, chiral phosphoric acid as a catalyst and reacting under the condition of a reaction solvent and an additive at room temperature; the reaction process is shown in the following formula:
wherein R1, R2, R3 and R4 are alkyl, aryl, halogen, nitro, hydroxyl, methoxy, acetyl and diazo.
2. The novel process for the synthesis of chiral triphenylmethane compounds according to claim 1, wherein the catalyst is used in an amount of 10% of the total mass of the reactants.
3. The novel process for the synthesis of chiral triphenylmethane according to claim 1, wherein the reaction solvent is one of toluene, fluorobenzene, trifluorotoluene, methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, diethyl ether, methylcyclopentyl ether, acetonitrile, xylene.
4. The novel process for synthesizing chiral triphenylmethane compounds according to claim 1, wherein the chiral phosphoric acid catalyst is selected from one of binaphthyl skeleton derivatives, octahydrobinaphthyl skeleton derivatives, spiroindene ring skeleton derivatives; the structural formula of the binaphthyl skeleton derivative is
Wherein G is selected from one of 2-naphthyl, 2,4, 6-triisopropylphenyl, 9-anthryl, 9-phenanthryl, 2,4, 6-trimethylphenyl and 3, 5-bis (trifluoromethyl) phenyl; the structural formula of the octahydrobinaphthyl skeleton derivative is +.>
Wherein G is selected from one of 1-naphthyl, 3, 5-di (trifluoromethyl) phenyl, 2,4, 6-triisopropylphenyl and 2,4, 6-trimethylphenyl; the structural formula of the spiroindene ring skeleton derivative is +.>
G is selected from one of 1-naphthyl, 3, 5-di (trifluoromethyl) phenyl, 2,4, 6-triisopropylphenyl and 2,4, 6-trimethylphenyl.
5. The novel process for synthesizing chiral triphenylmethane compounds according to claim 1, wherein said chiral phosphoric acid catalyst has the structural formula of
Wherein G is selected from 2,4, 6-trimethylphenyl.
6. The novel process for the synthesis of chiral triphenylmethane compounds according to claim 1, wherein the reaction additive is sodium sulfate, magnesium sulfate,
Molecular sieves, & gt>
Molecular sieves, & gt>
One of the molecular sieves.
7. A novel process for the synthesis of chiral triphenylmethane compounds according to claim 1, wherein the molar mass ratio of compound 1 to compound 2 is 1:1.2.
8. The novel method for synthesizing chiral triphenylmethane compounds according to claim 1, wherein the specific reaction process is represented by the following reaction formula:
in a 10mL reaction tube, 1.0mL toluene was added, 0.1mmol of substrate 1a,0.12mmol of substrate 2a,0.01mmol of CPA and 100mg of anhydrous Na2SO4 were sequentially added to the reaction tube, and the reaction system was reacted at room temperature for 12 hours; after the TLC detection reaction is finished, column chromatography purification is directly carried out, and 3a can be obtained.
9. The novel method for synthesizing chiral triphenylmethane compounds according to claim 8, wherein the column chromatography is silica gel column chromatography, and the eluting machine adopts petroleum ether/ethyl acetate mixed solution with a volume ratio of 5:1.
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