GB2620465A - Synthesis method of indole organophosphorus compound - Google Patents

Synthesis method of indole organophosphorus compound Download PDF

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GB2620465A
GB2620465A GB2304417.5A GB202304417A GB2620465A GB 2620465 A GB2620465 A GB 2620465A GB 202304417 A GB202304417 A GB 202304417A GB 2620465 A GB2620465 A GB 2620465A
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indole
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Fu Jianping
Han Xiaodan
Xu Changjiang
Xia Jun
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Institute of Applied Chemistry Jiangxi Academy of Sciences
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Institute of Applied Chemistry Jiangxi Academy of Sciences
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract

A process for preparing an indole organophosphorus compound, comprising the steps (i) performing in an first solvent an aldol condensation reaction and dehydration reaction between an indole-2-carbaldehyde (A) and an acetophenone (B) in the presence of a base catalyst to provide an indolenoyl compound (C), wherein R1 is selected from 2-Me, 3-Me, 4-Me, 2-Cl, 3-Cl, 4-Cl and H; Ar1 is selected form 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 3-BrC6H4, 4-MeOC6H4, naphthalene, thionaphthene, furan and pyrrole; and (ii) performing in a second solvent an addition reaction between diphenylphosphine oxide and the indolenoyl compound (C) in the presence of a metal salt catalyst to form the indole organophosphorus compound (D). The first solvent may be selected from ethanol, methanol, dichloromethane, and ethyl acetate. The base catalyst of step (i) may be sodium hydroxide or potassium hydroxide. The second solvent my be selected from dichloromethane, toluene, DMF, and n-hexane. The metal salt catalyst of step (ii) may be selected from Cs2CO3, Na2CO3, NaHCO3, K2CO3, K3PO4, Na3PO4 and Cu(OAc)2. Example compounds prepared include 3-(1,6-dimethyl-1H-indol-2-yl)-3-(diphenylphosphoryl)-1-phenylpropan-1-one; 3-(diphenylphosphoryl)-1-(4-methoxyphenyl)-3-(1-methyl-1H-indol-2-yl)propan-1-one; 1-(benzo[b]thiophen-2-yl)-3-(diphenylphosphoryl)-3-(1-methyl-1H-indol-2-yl)propan-1-one; 3-(diphenylphosphoryl)-3-(1-methyl-1H-indol-2-yl)-1-(1H-pyrrol-2-yl)propan-1-one.

Description

SYNTHESIS METHOD OF INDOLE ORGANOPHOSPHORUS COMPOUND
TECHNICAL FIELD
[0001] The present disclosure belongs to the technical field of organic chemical synthesis, and in particular relates to a synthesis method of an indole organophosphorus compound.
BACKGROUND
[0002] Organophosphorus compounds are widely used in organic synthesis, medicine, pesticides, materials and life sciences because of unique physical and chemical properties thereof With antibacterial, antitumor and other pharmacological activities, phosphorus-containing organic molecules are used as the main active ingredients of drugs such as tissue inhibitors of metalloproteinases (TIMPs), antimalarial drugs, and calcium antagonists. Some organic organophosphorus compounds exist in natural products. For example, Bialaphos is a tripeptide natural product isolated and purified from the fermentation broth of Streptomyces hygroscopicus, which is a non-selective herbicide; Fosfomycin, originally isolated from ASTtreptornyces fintlicle, is effective against Gram-positive and negative bacteria, which is a widely used commercial antibiotic. Organic organophosphorus compounds further play an important role in the field of functional materials. Organophosphorous flame retardants, which have been extensively studied and used, are generally accepted in the field of flame retardant materials because of halogen-free, non-toxic and high-efficiency characteristics thereof [0003] In another aspect, compounds containing indole ring structure exhibit excellent bioactivity in antihypertensive, antiproliferative, antiviral, antitumor, analgesic, anti-inflammatory, and antibacterial drugs due to the unique chemical structure thereof For example, vincaleucoblastine (VLB), a derivative of 3,3'-diindolylmethane, acts on tubulin to affect the mitosis of tumor cells, thereby inhibiting the proliferation of tumor cells. Melatonin is a typical indole hormone, which is a physiological tumor suppressor.
[0004] In view of the importance of organophosphorus compounds and indole ring skeletons, one of the research priorities of organic synthesis and pharmacology is how to efficiently and quickly construct novel molecules containing both organophosphorus and indole ring active units to achieve efficient fusion of active groups, thereby enhancing potential biological activity thereof The Michaelis-Arbuzov reaction developed early is the main method for the synthesis of phosphorus-containing compounds through C-P bond construction, that is, trivalent phosphates and halogenated hydrocarbons undergo bimolecular nucleophilic substitution reaction (SN2) to yield pentavalent alkyl phosphates, but the disadvantages of poor atom economy, harsh reaction conditions, and narrow substrate range limit the application of this reaction in the synthesis of organophosphorus compounds.
100051 P-H bond addition to olefinic bond and acetylenic bond hydrophosphination are an excellent way to construct a C-P bond. Direct construction of organophosphorus compounds phosphorus-hydrogen compounds can avoid the use of phosphorus-halogen reagents sensitive to water and oxygen, and the reaction is higher in atom economy, greener and more environmentally friendly. Such addition reactions are generally carried out under the catalysis of bases, metal catalysts or radical initiators, but these synthesis methods still have defects of expensive catalysts, requirement of anhydrous and oxygen-free reaction conditions, and more by-products.
SUMMARY
[0006] To solve the above problems, an objective of the present disclosure is to provide an efficient, economical and environmentally friendly synthesis method of an indole organophosphorus compound [0007] To achieve the above objective, the present disclosure adopts the following technical solution: 100081 A synthesis method of an indole organophosphorus compound is provided, including the following steps: [0009] step Si, dissolving an indole-2-carbaldehyde compound A and an acetophenone compound B as raw materials in a first solvent, and conducting aldol condensation and dehydration reactions in the presence of a base catalyst to yield an indolenoyl compound C; where 100101 a reaction route is as follows: 100111 Base catalyst First solvent
A
[0012] where R1 is one selected from the group consisting of 2-Me, 3-Me, 4-Me, 2-C1, 3-C1, 4-C1, and 1-1, Ai' is one selected from the group consisting of 2-MeC6H4, 3-MeC6H4, 4-MeC61-14, 3-BrC61-14, 4-Me0C6H4, naphthalene, thianaphthene, furan, and pyrrole; and [0013] step 52, dissolving diphenylphosphine oxide and the indolenoyl compound C obtained in step S1 in a second solvent, and conducting an addition reaction in the presence of a metal salt catalyst to yield a target product D; where [0014] a reaction route is as follows: [0015] p, Metal salt catalyst + Ph b- I
-
Second solvent
N / Ph Ph D.
[0016] Further, in the foregoing step Si, the indole-2-carbaldehyde compound A and the acetophenone compound B may be in a molar ratio of 1:2 to 2:1, and the indole-2-carbaldehyde compound A, the first solvent, and the base catalyst may be used in a ratio of 1 mmol: 5-15 mL. 1-2 mmol.
[0017] Further, in the foregoing step Sl, the first solvent may be one selected from the group consisting of ethanol, methanol, dichloromethane, and ethyl acetate.
[0018] Furthcr, in thc foregoing step Si, the basc catalyst may be a 0.5-1.5 mol/L NaOH or KOH solution.
[0019] Further, in the foregoing step Si, a reaction temperature may be in a range of 0°C to room temperature, and reaction time may be in a range of 1.5-3 h. [0020] Further, in the foregoing step 52, the diphenylphosphine oxide and the indolenoyl compound C may be in a molar ratio of 1:1 to 5:1, and the indolenoyl compound C, the second solvent, and the metal salt catalyst may be used in a ratio of 1 mmol: 2-8 mL: 1-5 mmol. [0021] Further, in the foregoing step S2, the second solvent may be one selected from the group consisting of dichloromethane, toluene, N,N-dimethylformamide, and n-hexane.
[0022] Further, in the foregoing step S2, the metal salt catalyst may be one selected from the group consisting of Cs2CO3, Na2CO3, NaHCO3, K2CO3, K3PO4, Na3PO4, and Cu(OAc)2. [0023] Further, in the foregoing step S2, the reaction temperature may be room temperature, and the reaction time may be in a range of 2-5 h. [0024] Further, according to the synthesis method of an indole organophosphorus compound, in step 52, a reaction process is monitored by thin layer chromatography (TLC), and after reactants completely disappear, a reaction mixture is poured into water and extracted with an extractant, and extracts are combined; the extracts are dried over a desiccant, filtered, and distilled under reduced pressure to obtain a crude product; and the crude product is purified by flash column chromatography to obtain a target compound.
100251 Further, the foregoing extractant may be one selected from the group consisting of dichloromethane, ethyl acetate, ether, and chloroform.
100261 Further, the foregoing desiccant may be one selected from the group consisting of anhydrous sodium sulfate, anhydrous calcium chloride, and anhydrous magnesium sulfate. 100271 Further, during purification by the foregoing flash column chromatography, an eluant may be petroleum ether and ethyl acetate, and the petroleum ether and the ethyl acetate may be in a volume ratio of 1:1.
100281 Because the foregoing technical solution is adopted, the present disclosure has the following advantages: 100291 According to the synthesis method of an indole organophosphorus compound provided by the present disclosure, an indole-2-carbaldehyde compound, as a starting material, undergoes aldol condensation and dehydration reactions with an acetophenone compound to yield asymmetric olefins with an indole skeleton, namely, indolenoyl compounds; a metal salt is used to catalyze the nucleophilic addition reaction of a 2-alkenyl indol one compound with a P-H bond of diphenylphosphine oxide to construct a C(sp3)-P bond to yield an indole organophosphorus compound. With the advantages of wide sources of raw materials, diverse structures, easy operation, low cost, simplicity, safety, mild conditions, rapid reaction, excellent atom economy, high yield, greenness, and high efficiency, the synthesis method has broad application prospects in the field of organic synthesis, providing a new route to synthesise complex phosphine ligands and bioactive organophosphorus compounds.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0030] The present disclosure can be further described in detail with reference to the following examples; however, the following examples are merely illustrative, and the present disclosure is not limited thereto
100311 Example 1
100321 Step 1, 2 mmol acetophenone compound B1 was added to a 25 mL round-bottomed flask, dissolved with 9 mL of ethanol, slowly added with 4 mL of 0.5 mol/L NaOH solution dropwise at 0°C, and stirred to react at room temperature for 1 h; 2 mmol indole-2-carbaldehyde compound Al was added and stirred to react at room temperature for 1 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1 85 mmol indolenoyl compound C I. [0033] the specific reaction formula is: Ethanol [0034] [0035] Al B1 C1 [0036] Step 2, 1.5 mmol diphenylphosphine oxide and 0.5 mmol prepared indolenoyl compound Cl were added to a 25 mL round-bottomed flask, dissolved with 1 mL of dichloromethane, stirred with 1 mmol Cs2CO3 to react at room temperature (rt.) for 2 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with dichloromethane (3 x 10 mL); the extracts were combined, dried over anhydrous sodium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D1 was obtained, with a yield of 92%.
[0037] The specific reaction formula is: 4-Pb CH,CO3 CAI,C1+, E" [0038] Ph/ Ph Cl D1 [0039] The 1H NMR (CDC13, 400 MHz) of the target product Di was as follows: 67.84-7.80 (m, 214), 7.76 (d, J= 7.8, 2H), 7.50-7.38 (m, 41-1), 7.29 (m, 5H), 7.21 (s, 1H), 7.13 (td, J= 7.6, 2.8 Hz, 2H), 6.91 (dd, J= 24, 8.8 Hz, 2H), 6.50 (d, J= 3.2 Hz, 1H), 4.52 (t, J= 8.8 Hz, 1H), 4.06 (ddd, ./= 18.0, 10.4, 4.0 Hz, 1H), 3.46 (ddd, ./-= 18.0, 9.2 2.0 Hz, 1H), 3.24 (s, 3H), and 2.31 (s, 3H); [0040] the 13C NMR (100 MHz, CDCI3) of the target product D1 was as follows: 6 196.70 (d, J = 12.9 Hz), 135.83 (d, 82.4 Hz), 134.65 (d, J= 4.8 Hz), 133.45, 132.35 (d, J = 2.5 Hz), 131.93 (d, = 2.6 Hz), 131.17 (d, ./= 9.1 Hz), 129.02 (d, = 11.2 Hz), 128.58 (d, ./ = 4.3 Hz), 128.21 (d, J= 11.7 Hz), 128.12, 127.72 (d, J= 2.7 Hz), 122.84, 119.95, 108.80, 101.61 (d, J= 5.1 Hz), 39.91, 34.22 (d, J= 70.5Hz), 30.23 (d, J= 110.3 Hz), 21.36; and [0041] the 31P NMR (162 MHz, CDCb) of the target product D1 was as follows: 631.26.
[0042] Example 2
[0043] Step 1, 2 mmol acetophenone compound B2 was added to a 25 mL round-bottomed flask, dissolved with 8 mL of ethanol, slowly added with 1.8 mL of 0.7 mol/L NaOH solution dropwise at 5°C, and stirred to react at room temperature for 1 h; 1 mmol indole-2-carbaldehyde compound A2 was added and stirred to react at room temperature for 50 mm, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 0.93 mmol indolenoyl compound C2.
[0044] The specific reaction formula is: NCiH Ethanol [0045] A2 B2 C2 [0046] Step 2,2.0 mmol diphenylphosphine oxide and 1.0 mmol prepared indolenoyl compound C2 were added to a 25 mL round-bottomed flask, dissolved with 3 mL of dichloromethane, stirred with 2.0 mmol Cs2CO3 to react at room temperature (r.t.) for 2.5 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with dichloromethane (3 > 10 mL); the extracts were combined, dried over anhydrous calcium chloride, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D2 was obtained, with a yield of 93%.
[0047] The specific reaction formula is: [0048] C11C1, + C2 D2 [0049] The 111NMR (400 MHz, CDCI3) of the target product D2 was as follows: 6 7.75-7.81 (m, 2H), 7.75 (d, J 7.6, 211), 7.50-7.39 (m, 5H), 7.32-7.28 (m, 5H), 7.14 (td, J = 7.6, 2.8 Hz, 2H), 6.82 (s, 1H), 6.79 (d, J = 8 Hz, 1H), 6.53 (d, J = 2.4 Hz, 1H), 4.53 (t, J = 8.8 Hz, 1H), 3.96 (ddd, J= 18.0 10.8 4.0 Hz, 1H), 3.46 (ddd,J= 18.0, 9.2, 1.6 Hz, 1H), 3.24 (s H), 2.35 (s, 3H); [0050] the 13C NMR (100 MITz, CDCI3) of the target product D2 was as follows: 6 195.67 (d, J= 12.9 Hz), 136.31 (d, J= 11.2 Hz), 132.92(d, 1=4,5 Hz), 132.38, 131.28 (d, 1=2,3 Hz), 131.93 (d, 1=2.5 Hz), 130.70(d, .1= 7.7 Hz), 120.12 (d, .1= 9.2 Hz), 129.89, 127.97 (d, 11.2 Hz), 127.53, 127.23, 127.11 (d, J=4.3 Hz), 124.51 (d, J=2.1 Hz), 120.09, 118.88, 108.09, 100.97 (d, J= 5.2 Hz), 38.94, 33.04 (d, J= 70.7 Hz), 28.66 (d,J= 68.0 Hz), 20.84; and 100511 the 31P NMR (162 MHz, CDCb) of the target product D2 was as follows: 631.31. [0052] Example 3 [0053] Step 1, 3 mmol acetophenone compound B3 was added to a 25 mL round-bottomed flask, dissolved with 13 mL of methanol, slowly added with 3.0 mL of 1.0 mol/L KOH solution dropwise at 10°C, and stirred to react at room temperature for 1.2 h; 2.5 mmol indole-2-carbaldehyde compound A3 was added and stirred to react at room temperature for 40 min, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 2.34 mmol indolenoyl compound C3. [0054] The specific reaction formula is: Kt-At Methanol [0055] A3 B3.3 [0056] Step 2, 2.5 mmol diphenylphosphine oxide and 1.0 mmol prepared indolenoyl compound C3 were added to a 25 mL round-bottomed flask, dissolved with 4 mL of toluene, stirred with 2.0 mmol Na2CO3 to react at room temperature (r.t.) for 2.5 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ethyl acetate (3 x 10 mL); the extracts were combined, dried over anhydrous sodium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D3 was obtained, with a yield of 91%.
[0057] The specific reaction formula is: [0058] C3 D3 [0059] The 1H NMR (400 MHz, CDC13) of the target product D3 was as follows: 6 7.85-7.81 (m, 2H), 7.77 (d, J= 8.0, 2H), 7.64-7.59 (m, 3H), 7.42-7.38 (m, 4H), 7.30-7.26 (m, 314), 7.157.13 (m, 2H), 6.80 (t, J= 7.6 Hz, 1H), 6.73 (d, J= 6.4 Hz, 1H) 6.56 (s, 1H), 4.53 (t, J= 9.6 Hz, 1H), 3.96 (ddd, J= 18.0, 10.8, 4.0 Hz, 11), 3.51 (s, 3H), 3.46 (dd, J =17.6, 9.2 Hz, 1H), 2.51 (s, 3H); [0060] the 1-3C, NMR (100 MHz, CDC13) of the target product D3was as follows: 5 196.78 (d, J = 13.0Hz), 136.21 (d, J = 11.4 Hz), 134.87(d, J= 4.7 Hz), 133.48 132.39 (d, J = 2.8 Hz), 131.90 (d, .1 = 2.6 Hz), 131.78 (d, .1= 8.4 Hz), 131.20 (d, .7= 11.4 Hz), 130.78 (d, .1= 11.4 Hz), 129.02 (d, J = 3.6 Hz), 128.91 (d, 1= 5.3 Hz), 128.60, 128.46 (d, J = 2.3 Hz), 128.26, 128.14, 124.51, 120.61, 119.41, 118.56, 102.98 (d, J = 5 Hz), 39.78, 34.01 (d, J= 70.3 Hz), 32.06 (d, J= 235.6 Hz), 20.52; and [0061] the 31P NMR (162 MHz, CDCb) of the target product D3 was as follows: 631.51. [0062] Example 4 [0063] Step 1, 2 mmol acetophenone compound B4 was added to a 25 mL round-bottomed flask, dissolved with 12 mL of ethanol, slowly added with 3.5 mL of 1.0 mol/L NaOH solution dropwise at 15°C, and stirred to react at room temperature for 1 h; 2.5 mmol indole-2-carbaldehyde compound A4 was added and stirred to react at room temperature for 1 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 236 mmol indolenoyl compound C4.
[0064] The specific reaction formula is: [0065] Ethanol A4 B4 C4 [0066] Step 2, 3.5 mmol diphenylphosphine oxide and 1.0 mmol prepared indolenoyl compound C4 were added to a 25 mL round-bottomed flask, dissolved with 3 mL of dichloromethane, stirred with 2.0 mmol Cs2CO3 to react at room temperature (r.t.) for 3 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ethyl acetate (3 x 10 mL); the extracts were combined, dried over anhydrous sodium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D4 was obtained, with a yield of 89%.
100671 The specific reaction formula is: [00681 (l82C:03 C4 D4 [0069] The NMR (400 MHz, CDC13) of the target product D4 was as follows: 5 7.83-7.77 (m, 4H), 7.55-7.51 (m, 1H), 7.49-7.42 (m, 3H), 7.34-7.29 (m, 5H), 7.18-7.13 (m, 2H), 6.966.93 (m, I= 7.6 Hz, 3H), 6.65 (d, J= 7.0 Hz, 1H), 4.52 (t, 1=9.2 Hz, 1H), 3.98 (ddd, 1= 18.2, 11.2,4.0 Hz, IN), 3.46 (ddd, 1=18.2, 9.2, 2 Hz, 1H), 3.29 (s, 3W; [0070] the I:3C NMR (100 MHz, CDC13) of the target product D4 was as follows: 6 195.57 (d, = 12.8 Hz), 136.61, 135.03, 134.73 (d,1= 5.4 Hz), 132.57, 131.44 (d, J= 2.6 Hz), 131.04 (d, J = 2.6 Hz), 130.73 (d, J = 8.3 Hz), 130.14 (d, J = 11.4 Hz), 128.04 (d, J = 11.2 Hz), 127.62, 127.30 (d, J = 11.7 Hz), 127.12, 125.36, 124.51, 120.733, 118.25, 106.73, 99.64 (d, J = 5.0 Hz), 38.92, 33.36 (d, 1=69.8 Hz), 28.52; and [0071] the 31P NMR (162 MHz, CDC13) of the target product D4 was as follows: 630.93. [0072] Example 5 [0073] Step 1, 4 mmol acetophenone compound B5 was added to a 25 mL round-bottomed flask, dissolved with 15 mL of dichloromethane, slowly added with 2 mL of 1.0 mol/L KOH solution dropwise at 20°C, and stirred to react at room temperature for 1 h; 2 mmol indole-2-carbaldehyde compound AS was added and stirred to react at room temperature for 1.5 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1.90 mmol indolenoyl compound C5.
[0074] The specific reaction formula is: [0075] AS B5 C5 [0076] Step 2, 3.0 mmol diphenylphosphine oxide and 1.0 mmol prepared indolenoyl compound C5 were added to a 25 mL round-bottomed flask, dissolved with 4 mL of dichloromethane, stirred with 2.5 mmol Cs2CO3 to react at room temperature (r.t.) for 3.5 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ether (3 x 10 mL); the extracts were combined, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D5 was obtained, with a yield of 85% [0077] The specific reaction formula is: [0078] Ph-C5 D5 [0079] The 11-1NMR (400 MHz, CDC13) of the target product D5 was as follows: 6 7.81 (t, 8.8Hz, 21-1), 7.50 (d, .1= 7.2 Hz, 1H), 7.46-7.43 (m, 4H), 7.33-7.28 (m, 2H), 7.23-7.19 (t, .1= 7.2 Hz, IR), 7.17-7.08 (m, 4H), 7.05-7.02 (m, 3H), 6.99-6.95 (m, 1H), 6.56 (d, J= 2.4 Hz, tH), 4.52 (t, J= 9.0 Hz, 1H), 3.82 (ddd, J= 18.0, 10.8, 2.4 Hz, 1H), 3.41 (ddd, J=18.0, 9.6,2.4 Hz, 1H), 3.23 (s, 3H), 2.11 (s, 3H); [0080] the 1-3C NMR (100 MHz, CDC13) of the target product D5 was as follows: 6 199.38 (d, J = 14.6 Hz), 137.14, 135.94, 131.31, 130.90, 130.81 (d, J = 7.4 Hz), 130.65 (d, J = 9.3 Hz), 130.15 (d, J= 9.4 Hz), 127.93 (d, J= 10.4 Hz), 124.67, (d, J= 8.3 Hz), 120.22, 119.30, 118.37, 108.03, 101.24, 41.42, 33.57 (d, J= 59.3 Hz), 28.67 (d, .1= 11.4 Hz), 19.94; and [0081] the 31P NMR (162 MHz, CDCb) of the target product D5 was as follows: 630.98. [0082] Example 6 [0083] Step 1, 2 mmol acetophenone compound B6 was added to a 25 mL round-bottomed flask, dissolved with 10 mL of ethanol, slowly added with 2 mL of 0.5 mol/L NaOH solution dropwise at 0°C, and stirred to react at room temperature for 1 h, 1 mmol indole-2-carbal dehyde compound AG was added and stirred to react at room temperature for] h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 095 mmol indolenoyl compound Co. 100841 The specific reaction formula is: AG B6 CO 100861 Step 2, 1.5 mmol diphenylphosphine oxide and 1.0 mmol prepared indolenoyl compound CO were added to a 25 mL round-bottomed flask, dissolved with 1 mL of dichloromethane, stirred with 1 mmol NaHCO3 to react at room temperature (r.t.) for 2 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with dichloromethane (3 x 10 mL), the extracts were combined, dried over anhydrous sodium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product, the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D6 was obtained, with a yield of 88%.
100871 The specific reaction formula is: 100881 0 !! -1) Ph Cs2C0;, --N Ph ---1-'IN A C14411, rt. C6 D6
100891 The 1H NMR (400 MHz, CDC13) of the target product D6 was as follows: 67.96-7.83 (m, 2H), 7.66-7.60 (m, 211), 7.60-7.47 (m, 4H), 7.40-7.27 (m, 4H), 7.23 (d, .1 = 7.2 Hz, 1H), 7.17 (td, J = 7.8, 3.0 Hz, 211), 7.13-706(m, 2H), 7.01 (ddd, J = 7.8, 5.6, 2.4 Hz, 1H), 6.69(d, J= 2.8Hz, 1H), 4.61 (t, J= 8.6 Hz, 1H), 4.06 (ddd, J = 18.0, 10.6, 3.6 Hz, 1H), 3.46 (ddd, J= 18.0, 9.4, 2.0 Hz, 1H), 3.34 (s, 3H), and 2.31 (s, 3W; and [0090] the 13C NMR (100 MHz, CDC13) of the target product D6 was as follows: 6196.81 (d, J = 13.2 Hz), 138.46, 136.58 (d, J = 74.5 Hz), 134.70 (d, J = 5.6 Hz), 134.25, 132.37 (d, J = 2.4 Hz), 131.92 (d, J = 2.4 Hz), 131.72 (d, J= 8.4 Hz), 131.05 (d, J = 9.2 Hz), 129.01 (d, J= 11.2 Hz), 128.62 (d, J = 25.0 Hz), 128.21 (d, J = 11.8 Hz), 127.72 (d, J = 2.4 Hz), 125.29, 121.18, 120.30, 119.83, 109.07, 102.18 (d, .1 = 5.0 Hz), 40.01, 33.69 (d, .1 = 71.2 Hz), 29.07, and 21.21; and [0091] the 31P NMR (162 MHz, CDC13) of the target product D6 was as follows 631.46. [0092] Example 7 [0093] Step 1, 2 mmol acetophenone compound B7 was added to a 25 mL round-bottomed flask, dissolved with 15 mL of methanol, slowly added with 2.5 mL of 0.8 mol/L NaOH solution dropwise at 5°C, and stirred to react at room temperature for 1.5 h; 1.5 mmol indole2-carbaldehyde compound A7 was added and stirred to react at room temperature for 1 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1.41 mmol indolenoyl compound C7.
[0094] The specific reaction formula is: [0095] A7 B7 C7 [0096] Step 2, 2 mmol diphenylphosphine oxide and 1 mmol prepared indolenoyl compound C7 were added to a 25 mL round-bottomed flask, dissolved with 3 mL of NAdimethylformamide, stirred with 2 mmol Na2CO3 to react at room temperature (r.t.) for 3 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ethyl acetate (3 >< 10 mL); the extracts were combined, dried over anhydrous calcium chloride, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D7 was obtained, with a yield of 86%.
[0097] The specific reaction formula is: C7 D7 100991 The 1H NMR (400 MHz, CDCI3) of the target product D7 was as follows: 6 7.91 (t, 8.8Hz, 2H), 7.69 (d, = 8.4 Hz, 2H), 7.62-7.54 (m, 3H), 7.53-7.50 (m, 3H), 7.40-7.30 (m, 3H), 7.20 (td, J = 7.6, 2.8 Hz, 2H), 7.14-7.09 (m, 2H), 7.06-7.02 (m, 1H), 6.67 (d, J = 2.4 Hz, 1H), 4.58 (t, J= 9.2 Hz, 1H), 4.00 (ddd, J= 18.0, 10.8, 4.4 Hz, 1H), 3.47 (ddd, J=18.0, 9.2, 1.6 Hz, 1H), 3.34 (s, 3H); 101001 the 13C NMR (100 MHz, CDCI3) of the target product D7 was as follows: 6 195.80 (d, J = 13.0 Hz), 136.92, 134.51 (d, J = 4.9 Hz), 132.45 (d, J = 2.6 Hz), 132.01 (d, J = 2.6 Hz), 131.73 (d, J= 8.4 Hz), 13110 (d, J= 9.2 Hz), 130.85, 130.49, 129.61, 129.08 (d, J= 11.2 Hz), 128.78, 128.29 (d, 1= 11.6 Hz), 127.64 (d, J= 2.4 Hz), 121.30, 119.45, 109.09, 102.13 (d, .1= 5.1 Hz), 39.87, 34.15 (d, J= 70.2114, 29.08; and 101011 the 31P NMR (162 MHz, CDCI3) of the target product D7 was as follows 631.09. 101021 Example 8 101031 Step 1, 2 mmol acetophenone compound B8 was added to a 50 mL round-bottomed flask, dissolved with 20 mL of ethanol, slowly added with 2.5 mL of 1.0 mol/L KOH solution dropwise at 10°C, and stirred to react at room temperature for 1 h; 2 mmol indole-2-carbaldehyde compound AS was added and stirred to react at room temperature for 1.5 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1.86 mmol indolenoyl compound C8.
[0104] The specific reaction formula is: N,N-dimethylformamide, r.t.
[00981 KOH Ethanol [01051 AS B8 C8 1:3 [0106] Step 2, 3 mmol diphenylphosphine oxide and 1 mmol prepared indolenoyl compound C8 were added to a 25 nth round-bottomed flask, dissolved with 2 mL of N,Ardimethylformamide, stirred with 2 mmol K2CO3 to react at room temperature (r.t.) for 3 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ether (3 < 10 mL); the extracts were combined, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product D8 was obtained, with a yield of 84%.
[0107] The specific reaction formula is: [0110] The 1H NMR (400 MHz, CDC13) of the target product D8 was as follows: 67.91 (t, 8.8 Hz, 2H), 7.60 (d, = 6.8 Hz, 1H), 7.57-7.51 (m, 3H), 7.46 (d, = 8.0 Hz, 1H), 7.40-7.28 (m, 5H), 7.23-7.19 (td, J = 7.6, 2.8 Hz, 2H), 7.15-7.09 (m, 2H), 7.06-7.02 (m, 2H), 6.67 (d, J = 2.4 Hz, 1H), 4.61 (t, J= 9.2 Hz, 1H), 3.82 (ddd, J = 18.0, 10.8, 4.0 Hz, 1H), 3.78 (s, 3H), 3.51 (ddd, J = 18.0, 9.6, 1.6 Hz, 1H), and 3.34 (s, 3H); [0111] the 13C NMR (100 MHz, CDCI3) of the target product D8 was as follows: 6 196.56 (d, 1= 13.1 Hz), 159.77, 137.51, 136.93, 134.66 (d, J= 5.1 Hz), 132.40 (d, J 2.7Hz), 131.96 (d, J= 2.6 Hz), 131.75 (d, J= 8.3 Hz), 131.12(d, J = 9.2 Hz), 129.61, 129.05 (d, J= 11.2 Hz), 128.27 (d, J= 11.6 Hz), 127.69(d, J = 2.4 Hz), 121.21, 120.83, 120.29, 119.38, 112.02, 109.08, 102.17 (d, J = 51 Hz), 55.45, 40.07, 34 19, 33.48, 29.71, 29.07; and [0112] the 31P NMR (162 MHz, CDC13) of the target product D8 was as follows: 631.22. [0113] Example 9 [0114] Step 1, 1.5 mmol acetophenone compound B9 was added to a 25 mL round-bottomed flask, dissolved with 12 mL of dichloromethane, slowly added with 2 mL of 1.0 mol/L KOH solution dropwise at 15°C, and stirred to react at room temperature for 1.5 h; 1 mmol indole2-carbaldehyde compound A9 was added and stirred to react at room temperature for 1.5 h, a [0109] C8 D8 N,N-dimethylformamide, r.t.
[0108] large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 0.92 mmol indolenoyl compound C9. [0115] The specific reaction formula is: [0116] A9 B9 C9 [0117] Step 2, 4 mmol diphenylphosphine oxide and 1 mmol prepared indolenoyl compound C9 were added to a 25 mL round-bottomed flask, dissolved with 2 mL of n-hexane, stirred with 3 mmol K3PO4 to react at room temperature (r.t.) for 3.5 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with chloroform (3 10 mL); the extracts were combined, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1: thus, the target product D9 was obtained, with a yield of 81%.
[0118] The specific reaction formula s: Dichloromethane [0119] K:Pth n-Hexane, r.t. C9 D9
[0120] The 1H NMR (400 MHz, CDC13) of the target product D9 was as follows: S 8.42 (s, 1H), 7.98 (t, ./= 8.4 Hz, 211), 7.91-7.85 (m, 2H), 7.78-7.76 (m, 2H), 7.59-7.48 (m, 6H), 7.38- 7.32 (m, 3H), 7.20-7.16 (td, J = 7.6, 2.8 Hz, 2H), 7.11-7.100, 2H), 7.05-7.00 (m, 1H), 6.78 (d, ./= 2.4 Hz, 1H), 4.69 (t, 1=8.8 Hz, 1H), 4.28 (ddd, .7= 18.0, 11.2, 4.0 Hz, 1H), 3.63 (ddd, J = 17.6, 9.2, 1.2 Hz, 111), 3.72 (s, 3H); [0121] the "C NMR (100 MHz, CDC13) of the target product D9 was as follows: 6 196.56 (d, J = 13.0 Hz), 136.95, 135.69, 134.70 (d, J = 4.7 Hz), 133.45, 132.46 (d, J = 7.6 Hz), 132.37, 129.13 (d, J = 11.2 Hz), 128.75, 128.46, 128.30 (d, J = 11.6 Hz), 127.71, 126.91, 123.48, 121.22, 120.34, 119.40, 109.10, 102.22 (d, J = 5.3 Hz), 39.95, 34.12 (d, J = 70.4 Hz), 29.12; and 101221 the 3113 NMR (162 MHz, CDCI3) of the target product D9 was as follows: 631.52. 101231 Example 10 101241 Step 1, 2 mmol acetophenone compound B10 was added to a 50 mL round-bottomed flask, dissolved with 25 mL of ethanol, slowly added with 2 mL of 1.5 mol/L NaOH solution dropwise at 20°C, and stirred to react at room temperature for 1 h; 2 mmol indole-2-carbaldehyde compound A10 was added and stirred to react at room temperature for 1 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1.81 mmol indolenoyl compound C10. 101251 The specific reaction formula is: 10126] A10 B 10 C10 101271 Step 2, 5 mmol diphenylphosphine oxide and 1 mmol prepared indolenoyl compound C10 were added to a 25 mL round-bottomed flask, dissolved with 5 mL of dichloromethane, stirred with 5 mmol Na3PO4 to react at room temperature (r.t.) for 4 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with ethyl acetate (3 x 10 mL); the extracts were combined, dried over anhydrous calcium chloride, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product DID was obtained, with a yield of 73%.
101281 The specific reaction formula is: Nn9PO4 r.t.
N r-Ta) N. Ph
CIO DIO
[0130] The 1H NMR (400 MHz, CDC13) of the target product DID was as follows: 67.89-7.86 (m, 2H), 7.78 (d, J= 8.0 Hz, 1H), 7.72 (d, J= 8.0 Hz, 1H), 7.54-7.45 (m, 4H), 7.37-7.27 (m, 4H), 7.19 (s, 1H), 7.15-7.11 (m, 2H), 7.05-7.02 (m, 2H), 6.98-6.94 (m, 1H), 6.69 (d, .1= 2.4 Hz, 1H), 4.54(t, 1 = 8.8 Hz, 1H), 4.08 (ddd,J= 17.6, 11.2, 4.0 Hz, 111), 3.49 (ddd, 1 = 17.2, 8.8, 1.2 Hz, 1H), and 3.26 (s, 3H); [0131] the 13C NMR (100 MHz, CDC13) of the target product DIO was as follows: 6 190.18, 141.56, 137.90, 136.95, 135.93, 131.45 (d, 1= 2.7 Hz), 130.99 (d,"1 = 2.5 Hz), 130.73 (d, 1= 8.3 Hz), 130.04 (d, .1= 9.2 Hz), 128.46, 128.10 (d, .1= 11.2 Hz), 127.28 (d, I = 11.7 Hz), 126.65, 125.10, 124.05, 121.84, 120.26 119.32, 118.39, 108.08, 101.31, 39.24, 33.10 (d, J= 69.9 Hz), 28.68 (d, J= 63.6 Hz); and [0132] the 31P NMR (162 MHz, CDCb) of the target product D10 was as follows 631.14. [0133] Example 11 [0134] Step 1, 2 mmol acetophenone compound B11 was added to a 50 mL round-bottomed flask, dissolved with 30 mL of ethanol, slowly added with 2.5 mL of 1.5 mol/L NaOH solution dropwise at 20°C, and stirred to react at room temperature for 2.5 h; 2 mmol indole-2-carbaldehyde compound All was added and stirred to react at room temperature for 0.5 h, a large amount of yellow solid was formed, filtered, and washed with ethanol, and the solvent was distilled off under reduced pressure to obtain 1.80 mmol indolenoyl compound C 1 1. [0135] The specific reaction formula is: [0136] All B11 C11 [0137] Step 2, 5 mmol diphenylphosphine oxide and 1 mmol prepared indolenoyl compound C11 were added to a 25 mL round-bottomed flask, dissolved with 8 ml. of toluene, stirred with 3 mmol Cu(OAc)2 to react at room temperature (r.t.) for 3 h; after monitoring the disappearance of the reaction substrate, the reaction mixture was poured into water and extracted thrice with dichloromethane (3 >< 10 mL); the extracts were combined, dried over anhydrous sodium sulfate, and filtered, and the solvent was distilled off under reduced pressure to obtain a crude product; the crude product was purified by flash column chromatography, and the eluant was petroleum ether and ethyl acetate in a volume ratio of 1:1; thus, the target product Dll was obtained, with a yield of 71%.
[0138] The specific reaction formula is:
HN
[0139]
FIN - 0 +-
Cu(OAc)2 r Ph C I I Dll [0140] The Ill NMR (400 MHz, CDCI3) of the target product Dll was as follows: 67.91 (t, 8.8 Hz, 211), 7.61-7.50 (m, 411), 7.39-7.30 (m, 4H), 7.20-7.19 (m, 2H), 7.13-7.07 (m, 211), 7.057.01 (m, 1H), 6.93 (s, IH), 6.88 (s, 111), 6.72 (d, 1= 1.6 Hz, 1H), 6.19 (s, IH), 4.61 (t, = 9.2 Hz, 1H), 3.47 (ddd, J= 16.4, 11.4, 4.0 Hz, 1H), 3.32 (d, 1H), and 3.28 (s, 3H); [0141] the i3C NMR (100 MHz, CDCI3) of the target product DI I was as follows: 6 I 86.3 I (d, .1= 13.2 Hz), 136.90, 132.44 (d, I = 2.3 Hz), 132.02 (d, = 2.9 Hz), 131.81 (d, I = 8.5 Hz), 131.39, 131.08 (d, J= 9.2 Hz), 129.06 (d, J= 11.3 Hz), 128.29 (d, J= 11.6 Hz), 124.88, 121.17, 120.39, 119.33, 116.99, 110.97, 109.03, 102.48, 38.61, 34.05 (d, J = 70.2 Hz), 29.71 (d, J = 69 Hz); and [0142] the 31P NIVIR (162 MHz, CDCI3) of the target product Dll was as follows: 631.99. [0143] The above description is only preferred examples of the present disclosure, and is not intended to limit the present disclosure. Although the present disclosure is expounded with reference to the above examples, a person skilled in the art can still make modifications on the technical solution described in the above examples or equivalent substitutions on some technical features of the technical solution. Any modification, equivalent substitution, and improvement made within the spirit and principle of the present disclosure shall be included within the protection scope of the present disclosure.

Claims (9)

  1. WHAT IS CLAIMED IS: 1. A synthesis method of an indole organophosphorus compound, comprising the following steps: step SI, dissolving an indole-2-carbaldehyde compound A and an acetophenone compound B as raw materials in a first solvent, and conducting aldol condensation and dehydration reactions in the presence of a base catalyst to yield an indolenoyl compound C; wherein a reaction route is as follows: Base catalyst First solventAwherein RI is one selected from the group consisting of 2-Me, 3-Me, 4-Me, 2-C1, 3-C1, 4-C1, and H; Ai' is one selected from the group consisting of 2-MeC6lLi, 3-MeC6114, 4-MeC61-14, 3-BrC6H4, 4-Me0C6H4, naphthalene, thianaphthene, furan, and pyrrole; and step 52, dissolving diphenylphosphine oxide and the indolenoyl compound C obtained in step 51 in a second solvent, and conducting an addition reaction in the presence of a metal salt catalyst to yield a target product D; wherein a reaction route is as follows: ii P Metal salt catalyst + ph--1 ' ph)N-1 1 N H Second solvent R14N
  2. N Fr-0 / \ Ph Ph D. 2. The synthesis method of an indole organophosphorus compound according to claim 1, wherein in step S I, the indole-2-carbaldehyde compound A and the acetophenone compound B are in a molar ratio of 1:2 to 2:1, and the indole-2-carbaldehyde compound A, the first solvent, and the base catalyst are used in a ratio of 1 mmol: 5-15 mL* 1-2 mmol.
  3. 3. The synthesis method of an indole organophosphorus compound according to claim 1 or 2, wherein in step Si, the first solvent is one selected from the group consisting of ethanol, methanol, dichloromethane, and ethyl acetate.
  4. 4 The synthesis method of an indole organophosphorus compound according to claim 1 or 2, wherein in step Sl, the base catalyst is a 0.5-1.5 mol/L NaOH or KOH solution.
  5. 5. The synthesis method of an indole organophosphorus compound according to claim 1, wherein in step 51, a reaction temperature is in a range of 0°C to room temperature, and reaction time is in a range of 1.5-3 h.
  6. 6. The synthesis method of an indole organophosphorus compound according to claim 1, wherein in step S2, the diphenylphosphine oxide and the indolenoyl compound C are in a molar ratio of 1:1 to 5:1, and the indolenoyl compound C, the second solvent, and the metal salt catalyst are used in a ratio of 1 mmol: 2-8 mL-1-5 mmol.
  7. 7 The synthesis method of an indole organophosphorus compound according to claim 1 or 6, wherein in step S2, the second solvent is one selected from the group consisting of dichloromethane, toluene, N,N-dimethylformamide, and n-hexane.
  8. 8. The synthesis method of an indole organophosphorus compound according to claim 1 or 6, wherein in step 52, the metal salt catalyst is one selected from the group consisting of Cs2CO3, Na2CO3, NalIC03, 1C2CO3, K3PO4, Na3PO4, and Cu(OAc)2.
  9. 9. The synthesis method of an indole organophosphorus compound according to claim 1, wherein in step S2, the reaction temperature is room temperature, and the reaction time is in a range of 2-5 h The synthesis method of an indole organophosphorus compound according to claim 1, wherein in step S2, a reaction process is monitored by thin layer chromatography (TLC), and after reactants completely disappear, a reaction mixture is poured into water and extracted with an extractant, and extracts are combined; the extracts are dried over a desiccant, filtered, and distilled under reduced pressure to obtain a crude product; and the crude product is purified by flash column chromatography to obtain a target compound.
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Dalton Transactions, vol. 51, no. 21, 2022, pages 8350-8367 *
Inorganic Chemistry, vol. 60, no. 22, 2021, pages 17276-17287 *
Synlett, vol. 31, no. 13, 2020, pages 1295-1297 *
Tetrahedron Letters, vol. 122, 2023, Article No. 154505 *

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