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Chemical Structure| 28957-04-2
Chemical Structure| 28957-04-2
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Product Details of [ 28957-04-2 ]

CAS No. :28957-04-2 MDL No. :MFCD00221762
Formula : C20H28O6 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 364.43 Pubchem ID :-
Synonyms :
NSC-250682;Isodonol;Oridonine;Rubescenin

Safety of [ 28957-04-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 28957-04-2 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 28957-04-2 ]

[ 28957-04-2 ] Synthesis Path-Downstream   1~59

  • 2
  • [ 28957-04-2 ]
  • [ 29288-74-2 ]
YieldReaction ConditionsOperation in experiment
87.8% With Jones reagent; In acetone; at 0℃; for 0.25h; General procedure: Compound 2 (72 mg, 0.2 mmol) was dissolved in acetone. To this solution Jones reagent was added dropwise until a red color persisted. The mixture was stirred at 0 C for 15 min and isopropanol was added. Then the mixture was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to give compound 3 (63 mg, 87%) as a white powder.
87% With Jones reagent; In acetone; at 0℃; for 0.25h; Compound 7 (72 mg,0.2 mmol) was dissolved in acetone. To this solution, Jones reagent was added dropwise until a red color persisted. The mixture was stirred at 0 .C for 15 min and isopropanol was added. Then the mixture was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to give compound 8 (63 mg, 87%) as white powder. Compound 8 (50 mg, 0.14mmol) was dissolved in THF (5 ml), and sodium carbonate (120 mg1.13 mmol) was added. Lead tetraacetate (212 mg, 0.5 mmol) was added as three portions with intervalsof 5 min. The reaction mixture was stirred at room temperature for 15 min, andthen insoluble matter was filtered. The mixture was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to givecompound 9 (48 mg, 95%) as white powder. The crude product 9 couldbe used for next step without further purification.
85% To 1.97 g (5 mmol) of <strong>[28957-04-2]oridonin</strong> was added 40 mL of acetone,0 C,Slowly drop 6 mL of Jone's reagent,Rose to room temperature, reaction 2h,Add 0.4mL isopropanol, reaction 0.5h,Then add 0.5gNaHCO3, reaction 0.5h,50 mL of ethyl acetate was added,Filtered, concentrated under reduced pressure, petroleum ether-acetone recrystallization,To give 1.69 g of solid in 85% yield.
82% With Jones reagent; In acetone; at 0℃; for 0.333333h; [091] To a stirring solution of <strong>[28957-04-2]oridonin</strong> (500 mg, 1.37 mmol) in acetone (40 mL) was added Jones reagent (0.6 mL) dropwise at ice-water bath. The resulting mixture was stirred at 0C for 20 mm, and isopropanol was added to quench excess Jones reagent. Then the mixture was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to give a solid crude product. The crude residue was recrystallized from acetone-hexane to give CYD-5-28 as a white solid (410 mg, 82%); mp 219-220 C (Lit. mp 219-221 C). 1H NMR (600 MHz, (CD3)2C0): oe 6.52 (br s, 1H), 6.10 (s, 1H), 5.62 (s, 1H), 5.41 (d, 1H, J= 10.8 Hz), 5.24 (s, 1H), 4.91 (s, 1H), 4.22 (d, 1H,J= 10.2 Hz), 3.92 (d, 1H,J= 10.8 Hz), 3.69 (m, 1H), 3.31 (br s, 1H), 3.01 (d, 1H, J= 9.6 Hz), 2.76 (m, 5H), 2.46 (m, 1H), 2.36 (m, 1H), 2.19 (m, 1H), 1.92 (m, 3H), 1.68 (m, 1H), 1.61 (m, 1H), 1.19 (m, 1H), 1.14 (s, 3H), 0.97 (s, 3H).
71% With Jones reagent; In acetone; for 3h;Cooling with ice; Chromium trioxide (240 mg, 2.4 mmol) was dissolved in 2 mL water. 0.22 mL concentrated sulfuric acid was added at 0 C., followed by 3 mL of water. The mixture was stirred to form Jone's reagent for later use. To <strong>[28957-04-2]oridonin</strong> (730 mg, 2 mmol) was added 20 mL acetone to form a suspension. The Jone's reagent (2.4 mmol of chromium trioxide) was slowly added dropwise under ice-bath conditions. After being stirred for 3 hours, the reaction solution was returned to room temperature. The reaction was quenched with isopropanol and the acetone solvent was removed. The crude product was extracted three times with dichloromethane (30 mL*3). The organic phase was washed with saturated sodium bicarbonate followed by saturated saline solution, dried and rotavapped. The resulted crude product was separated via silica gel column (petroleum ether:ethyl acetate=1:1) to give 1-oxo <strong>[28957-04-2]oridonin</strong> (520 mg, 71% yield) as a white powder. Meanwhile, 100 mg of <strong>[28957-04-2]oridonin</strong> was recovered with the recovery rate being 14%. MS (m/z): 363 [M+H]+, 385 [M+Na]+.
With Jones reagent; Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.Compound 19: white solid, 24% yield, m.p. 114-116 C; IR (KBr) numax 3404, 2957, 2361, 1707, 1643, 1604,1508, 1458, 1280, 1242, 1155, 1080, 1051, 965, 909 cm1; 13C-NMR (DMSO-d6, 125 MHz), d (ppm) 211.47,205.02, 166.92, 164.25, 149.59, 132.39, 132.31, 126.06, 122.07, 115.67, 115.50, 96.91, 74.91, 73.46, 64.93,61.50, 59.87, 50.78, 48.59, 41.63, 38.41, 35.73, 32.84, 30.49, 30.06, 23.14, 19.20; 1H-NMR (CDCl3, 500 MHz), (ppm) 7.95 (2H, m, Ar-H), 7.06 (2H, d, J = 8.7 Hz, Ar-H), 6.30 (1H, s, 17-CH2), 6.10 (1H, s, 14-CH),5.64 (1H, s, 17-CH2), 5.48 (1H, d, J = 11.5 Hz, 6-OH), 4.34, 4.03 (each 1H, d, JA = JB = 9.5 Hz, 20-CH2),4.12 (1H, s, 7-OH), 3.77 (1H, m, 6-CH), 3.25 (1H, d, J = 9.9 Hz, 13-CH); MS (ESI) m/z: 485.2 [M + H]+,507.2 [M + Na]+, 523.2 [M + K]+.
With Jones reagent; In acetone; at 0℃; for 0.5h; The preparation of ADT-OH was according to previous literature [82]. <strong>[28957-04-2]Oridonin</strong> (1 g, 2.76 mmol) was added in 20 mL of acetone and cooled to 0 C. Jones reagent (3.2 mL, 8.28 mmol) was added dropwise and stirred at 0 C for 0.5 h. The mixturewas quenched by dropwise addition of isopropyl alcohol (1 mL) and extracted with DCM (3 30 mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and evaporated under reduced pressure to produce the crude compound 2. <strong>[28957-04-2]Oridonin</strong> (182 mg, 0.50 mmol) was added into 10 mL acetone, then mixed with TsOH (43.1 mg, 0.25 mmol), DMAP (30.5 mg, 0.25 mmol) and 2,2- dimethoxypropane (1.5 mL). The mixture was refluxed for 1.5 h and then concentrated in vacuo to get compound 4. 4 was dissolved in 5mL DCM and mixed with 0.5 mL TEA, DMAP (catalytic amount) and 0.75 mL Ac2O. After stirring at room temperature for 6 h, extracted with DCM (3 30 mL), washed with brine, dried over anhydrous Na2SO4, and evaporated to give compound 5. 5 was added to 10 mL of 10% HCl/THF (1:1) and the solutionwas stirred at room temperature for 4 h. Through post-processed as described above, compound 6 was got.
With Jones reagent; In acetone; for 0.333333h; The <strong>[28957-04-2]oridonin</strong> (500 mg, 0.73 mmol) was dissolved in acetone. Slowly add 1.2ml Jones reagent and react for 20min. The reaction was complete by TLC.It was washed three times with water, and the organic phase was dried over anhydrous magnesium sulfate and filtered to give a clear solution, which was evaporated to dryness with acetone and n-hexane to give 1-oxotoxin.The synthesis method of Example 1 was carried out using 1-oxotosine as a raw material.
With Jones reagent; In acetone; at 0℃; Dissolve 45 mg of ADT-OH (0.2 mmol) in anhydrous acetone, add 43 muL of 2-bromoethanol (0.6 mmol), 83 mg of potassium carbonate (0.6 mmol), and reflux for 8 h. After the reaction is completed, filter with suction. Analysis (petroleum ether: ethyl acetate = 4: 1) gave orange-red compound 2a.Dissolve 72mg (0.2mmol) of <strong>[28957-04-2]oridonin</strong> in acetone, add Jones reagent to oxidize until no new spots are generated, filter and evaporate the solvent to obtain 1-position of <strong>[28957-04-2]oridonin</strong>-4.Afterwards, 90 mg of compound 4 (0.25 mmol) was dissolved in 6 mL of anhydrous dichloromethane, 50 mg of succinic anhydride (0.50 mmol), 173 muL of triethylamine (1.25 mmol), a catalytic amount of DMAP were added, and the mixture was stirred at room temperature for 6 h.TLC monitors the reaction and stops the reaction when the reaction is complete or does not continue.After washing with water, the layers were separated, and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain compound 5a.74 mg of compound 5a (0.16 mmol) was dissolved in anhydrous dichloromethane, 92 mg of EDCI (0.48 mmol), a catalytic amount of DMAP, and 43 mg of compound 2a (0.16 mmol) were added sequentially, and the mixture was stirred overnight at room temperature.The reaction was monitored by TLC. After the reaction was completed, about 20 mL of water was added, extracted three times with dichloromethane, 10 mL each time, the organic phases were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and silica gel column chromatography (Dichloromethane: methanol = 200: 1) The orange-red target compound 6a was obtained with a yield of 33.2%.

  • 3
  • [ 28957-04-2 ]
  • [ 77-76-9 ]
  • [ 331282-94-1 ]
YieldReaction ConditionsOperation in experiment
93% With toluene-4-sulfonic acid; In acetone; at 20℃; for 2h; [0107] To a solution of <strong>[28957-04-2]oridonin</strong> (500 mg, 1.36 mmol) in acetone (20 mL) was added TsOH (20 mg) and 2,2-dimethoxypropane (3.0 mL) at ft The resulting mixture was stirred at rt for 2 hrs. After that, the reaction mixture was diluted with water and extracted with dichloromethane. The extract was washed with saturated NaHCO3 (aq.) solution and brine, dried over anhydrous Na2SO4, filtered, and evaporated to afford compound CYD-5-60 as a colorless gel (520 mg, 93%).
85% With toluene-4-sulfonic acid; In acetone; at 56℃; for 0.25h; Compound 1 (100 mg, 0.27 mmol) was dissolved in acetone (10 ml). TsOH and 2,2-dimethoxypropane (1 ml) were added to this solution. The mixture was stirred at 56 C for 15 min, and diluted with water and extracted with dichloromethane. The extract was washed with saturated NaHCO3 solution and brine, dried over anhydrous Na2SO4, filtered, and evaporated to afford compound 6 (94 mg, 85%) as a white powder: mp 204-206 C; IR (KBr) upsilonmax 3414, 1713, 1641 cm-1; -13.2 (c 0.14 CHCl3); 1H NMR (CDCl3) delta 6.15 (1H, s, 17-CH2), 5.77 (1H, d, J = 11.7 Hz, 6-OH), 5.56 (1H, s, 17-CH2), 4.79 (1H, s, 14-CH), 4.24, 4.04 (each 1H, dd, JA = JB = 9.9 Hz, 20-CH2), 3.90 (1H, m, 1-CH), 3.47 (1H, m, 6-CH), 3.06 (1H, d, J = 9.0 Hz, 13-CH), 1.65 (6H, s, -CH3), 1.15 (3H, s, -CH3), 1.12 (3H, s, -CH3); 13C NMR (DMSO-d6) delta 206.28, 151.46, 119.68, 100.10, 94.60, 72.74, 72.40, 70.04, 62.76, 58.78, 56.33, 50.52, 40.47, 38.73, 33.39, 30.38, 29.20, 25.75, 22.38, 19.62; ESIMS m/z 405.2 [M + H]+.
85% With toluene-4-sulfonic acid; In acetone; at 56℃; for 0.25h; Compound 7 (100 mg, 0.27 mmol) was dissolved in acetone (10 ml). TsOH and 2,2-dimethoxypropane (1ml) were added to this solution. The mixture was stirred at 56 C for 15 min, and diluted with water and extracted with dichloromethane. The extract was washed with saturated NaHCO3 solution and brine, dried over anhydrous Na2SO4, filtered, and evaporated to afford compound 11 (94 mg, 85%) as a white powder. Compound 11 (90 mg, 0.22 mmol) was dissolved in dichloromethane, DMAP and TEA (0.2 ml) were added.The mixture was stirred at room temperature for 2.5 h, and dilutedwith water and extracted with dichloromethane. The extract was washed withsaturated NaHCO3 solution and brine, dried over anhydrous Na2SO4,filtered, and evaporated to give compound 12 (94 mg, 95%) as a white powder. Ketal deprotection of 12 (50 mg, 0.11 mmol) was added to 10 ml of 10% HCl/THF (1:1) and the solution was stirred at room temperature for 1 h.Then the mixture was diluted with water and extracted with dichloromethane. The extract was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to give compound 13 (45 mg, 99%) as a white powder. Following the procedure described for preparation of compound 9, compound 14 was prepared from compound 13 as a white solid (97%).
With toluene-4-sulfonic acid; In acetone; at 56℃; Treatment of <strong>[28957-04-2]oridonin</strong> with 2,2-dimethoxypropane in presence ofp-TsOH in acetone afforded compound 5 in 87% yield. Compound 5upon reaction with Ac2O/C5H5N/Et3N/DMAP/CH2Cl2, yielded correspondingcompound 6 in 95% yield. Deprotection of compound 6with 1 M HCl gave the corresponding compound 8 in quantitativeyield: mp 249.3-250.6 C; 1H NMR (500 MHz, CDCl3) delta 6.17 (s, 1H),5.55 (s, 1H), 4.84 (s, 1H), 4.59 (dd, J = 11.2, 5.5 Hz, 1H), 4.25 (d,J = 10.4 Hz, 1H), 4.17 (d, J = 10.3 Hz, 1H), 3.79 (d, J = 7.4 Hz, 1H), 3.05(d, J = 9.6 Hz, 1H), 2.47-2.38 (m, 1H), 1.97 (s, 3H), 1.89-1.82 (m, 2H),1.78-1.71 (m, 1H), 1.61-1.52 (m, 1H), 1.45 (dd, J 15.6, 8.1 Hz, 2H),1.36-1.28 (m, 2H), 1.20 (t, J 7.6 Hz, 1H), 1.13 (d, J 5.9 Hz, 6H). 13CNMR (126 MHz, CDCl3) delta 207.31, 169.87, 150.93, 121.03, 96.98, 75.59,74.10, 72.37, 63.57, 61.76, 59.28, 53.08, 42.55, 39.79, 38.15, 33.46,32.65, 29.83, 29.66, 25.06, 21.94, 21.48, 18.17. HRESIMS m/z407.2058 [M+H]+ (calcd for C22H31O7 407.2064).
With dmap; toluene-4-sulfonic acid; In acetone; for 1.5h;Reflux; The preparation of ADT-OH was according to previous literature [82]. <strong>[28957-04-2]Oridonin</strong> (1 g, 2.76 mmol) was added in 20 mL of acetone and cooled to 0 C. Jones reagent (3.2 mL, 8.28 mmol) was added dropwise and stirred at 0 C for 0.5 h. The mixturewas quenched by dropwise addition of isopropyl alcohol (1 mL) and extracted with DCM (3 30 mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and evaporated under reduced pressure to produce the crude compound 2. <strong>[28957-04-2]Oridonin</strong> (182 mg, 0.50 mmol) was added into 10 mL acetone, then mixed with TsOH (43.1 mg, 0.25 mmol), DMAP (30.5 mg, 0.25 mmol) and 2,2- dimethoxypropane (1.5 mL). The mixture was refluxed for 1.5 h and then concentrated in vacuo to get compound 4. 4 was dissolved in 5mL DCM and mixed with 0.5 mL TEA, DMAP (catalytic amount) and 0.75 mL Ac2O. After stirring at room temperature for 6 h, extracted with DCM (3 30 mL), washed with brine, dried over anhydrous Na2SO4, and evaporated to give compound 5. 5 was added to 10 mL of 10% HCl/THF (1:1) and the solutionwas stirred at room temperature for 4 h. Through post-processed as described above, compound 6 was got.

  • 4
  • [ 28957-04-2 ]
  • [ 16763-48-7 ]
YieldReaction ConditionsOperation in experiment
99% With sodium periodate; In water; at 20℃; for 24h; Compound 1 (364 mg, 1 mmol) was dissolved in water (10 ml). To this solution was added sodium periodate (3.16 g, 14.8 mmol). The mixture was stirred at room temperature for 24 h and then extracted with dichloromethane. The dichloromethane layer was washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to give compound 2 (360 mg, 99%) as a white powder: mp 183-185 C; IR (KBr) upsilonmax 3450, 1754, 1645 cm-1; -80.3 (c 0.44 CHCl3); 1H NMR (DMSO-d6) delta 6.17 (1H, d, J = 3.3 Hz, 6-OH), 5.92 (1H, s, 17-CH2), 5.52 (1H, s, 17-CH2), 5.38 (1H, d, J = 2.1 Hz, 14-OH), 5.17 (1H, d, J = 2.1 Hz, 6-CH), 4.67 (1H, s, 14-CH), 4.65 (1H, m, 1-CH), 3.87, 3.58 (each 1H, dd, JA = JB = 9.1 Hz, 20-CH2), 2.95 (1H, d, J = 9.1 Hz, 13-CH), 2.49 (2H, m, 12-CH2), 1.67 (2H, m, 2-CH2), 1.36 (2H, m, 11-CH2), 1.26 (1H, m, 9-CH), 0.93 (3H, s, 18-CH3), 0.88 (3H, s, 19-CH3); 13C NMR (DMSO-d6) delta 200.30, 166.88, 150.42, 118.59, 100.73, 75.16, 72.81, 71.28, 62.18, 54.99, 53.78, 49.86, 47.67, 43.07, 36.44, 32.67, 30.70, 29.55, 23.22, 22.82, 18.75; ESIMS m/z 747.4 [2M + Na]+; HR-MS (ESI, M + H) m/z: calcd for C20H27O6: 363.1802, found 363.1799.
With sodium periodate; In water; at 20℃; <strong>[28957-04-2]Oridonin</strong> (1.08g, 3.0mmol) was dissolved in 50mL water then mixed with sodium periodate (2.57g, 12.0mmol) and stirred for 48h to give compound 2. The mixture was extracted by DCM (3×50mL). The organic layer was combined, washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Compound 2 (500mg, 1.4mmol) was dissolved in 50mL acetone, then Jones reagent (1700muL, 4.3mmol) was added dropwise at 0C to give compound 3 after 30min. Isopropanol was added to quench the reaction then poured into 20mL water, for extraction with DCM (3×20mL). The organic layer was combined, washed with brine, dried over anhydrous Na2SO4 and concentrated in vacuo. Enmein-type cores (36mg, 0.1mmol) were dissolved in 5mL DCM and conjugated with the corresponding nitrogen mustards (0.2mmol), using EDCI (0.4mmol) and DMAP (0.02mmol). The mixture was stirred for 8-12h under room temperature, then poured into 10mL 10% HCl and 10mL water, for extraction with DCM (3×10mL). The organic layer was combined, washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. The target products were obtained through purification by flash column chromatography (MeOH/DCM 1:200, v/v).
  • 5
  • [ 28957-04-2 ]
  • (4aR,5S,6S,6aR,9S,11aS,11bR,14R)-5,6,14-trihydroxy-4,4-dimethyl-8-methylene-4,4a,5,6,9,10,11,11a-octahydro-3H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-7(8H)-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% (A), oridenin (2 g, 5.49 mmol)Dissolved in anhydrous acetone (treated with phosphorus pentoxide) 30mL,Adding 1 mL of 2,2-dimethoxypropane and a catalytic amount of p-toluenesulfonic acid,Drying tube protection,Reflux reaction 10min,The solution is clarified by white turbidity,Add 0.2mL 2,2-dimethoxypropane,TLC monitoring reaction to disappearance of raw materials,Cold to room temperature,A saturated NaHCO3 solution was added,Dichloromethane extraction three times,Each time 50mL,Saturated salt washed twice,Dried over anhydrous sodium sulfate,filter,concentrate,To give 2.10 g of a white solid (95% yield)Can be used directly for the next step.(B), the product of (a) was dissolved in 30 mL of dichloromethane pre-dried (calcium chloride dry)Add 2 mL of triethylamine,Ice bath stirring,20 ml of 1 ml of methanesulfonyl chloride was added dropwise,Stirring was continued for 1 hour,TLC detection of raw materials disappeared,70 mL of dichloromethane was added,Washed twice,Saturated salt washed once,Each time 20mL,Dried over anhydrous sodium sulfate, concentrated,To give 2.01 g of a pale yellow solid (yield 80%).(C), (b) (2.01 g, 4.17 mmol) was dissolved in 20 mL of dry dry DMF,Lithium carbonate (3.08 g, 41.65 mmol) was added,Lithium bromide (3.62 g, 41.65 mmol),110 C for 1 hour,Cooled to room temperature,Sand core funnel filter to remove lithium carbonate,Lithium bromide,The solid was washed three times with dichloromethane,Combined organic layer,Add dichloromethane to 100ml,Washed twice,Saturated salt washed once,Wash the DMF, each 20ml, concentrated, with the pump to the residual DMF spin dry, dichloromethane column quickly obtained pale yellow solid 1.21g (yield 75%).(D), the product of (c) (1.21 g, 3.13 mmol)Was dissolved in 20 mL of tetrahydrofuran,Add 5 mL of 10% hydrochloric acid solution,Stirred at room temperature for 0.5 hour,Spin dry tetrahydrofuran,Add dichloromethane to 80mL,Washed once,Saturated salt washed once,Each 20 mL, concentrated, dichloromethane: methanol = 100: 1 column chromatography,To give 0.98 g of a white solid (yield 90%).
  • 6
  • [ 28957-04-2 ]
  • [ 830-09-1 ]
  • ent-1α,6β,7β-trihydroxy-(14β-O-p-methoxycinnamoyl)-15-oxo-7,20-epoxy-16-kaurene [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 18h; Synthesis of target compound Compound 1 (72 mg, 0.2 mmol) was mixed with 4-methoxycinnamic acid (0.22 mmol), EDCI (0.25 mmol) and DMAP (0.01 mmol) in 15 mL of dry dichloromethane and stirred at room temperature for 18 h. The mixture was poured into 15 mL of 10% HCl, and extracted with dichloromethane (10 mL * 3). The organic layer was combined, washed with water and saturated NaCl solutions sequentially, dried over anhydrous Na2SO4, and concentrated in vacuo. The crude product was purified by column chromatography (MeOH/CH2Cl2 1:150 v/v) to give the compound 2. ent-1alpha,6beta,7beta-trihydroxy-(14beta-O-p-methoxycinnamoyl)-15-oxo-7,20-epoxy-16-kaurene (Compound 2) 75% as white solid, mp. 175-177 C; 1H NMR (CDCl3, 300 MHz): delta (ppm) 7.59, 6.20 (dd, JA = JB = 15.9 Hz, each 1H), 7.44 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.7 Hz, 2H), 6.21 (m, 2H), 5.93 (s, 1H), 5.49 (s, 1H), 4.42 (s, 1H), 4.09, 4.35 (dd, JA = JB = 9.6 Hz, each 1H), 3.86 (s, 3H), 3.79 (m, 1H), 3.53 (m, 1H), 3.27 (m, 1H), 2.63 (m, 1H), 2.38 (m, 1H), 2.04 (m, 1H), 1.80 (m, 2H), 1.71 (m, 5H), 1.54 (m, 1H), 1.11 (s, 6H); 13C NMR (CDCl3, 75 MHz): delta (ppm) 206.3, 165.0, 161.4, 149.4, 145.8, 129.6, 126.0, 119.7, 113.9, 113.5, 95.8, 76.1, 72.9, 62.9, 61.4, 59.4, 54.9, 54.1, 40.9, 40.8, 38.2, 33.3, 32.0, 30.0, 29.5, 21.1, 19.2; MS (ESI) m/z: 525.3 [M + H]+; HR-MS (ESI) m/z: calcd for C30H37O8 [M + H]+ 525.2483, found 525.2493.
  • 7
  • [ 28957-04-2 ]
  • [ 80883-54-1 ]
  • C33H39NO9 [ No CAS ]
  • 8
  • [ 28957-04-2 ]
  • [ 124-07-2 ]
  • C28H42O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
38% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 9
  • [ 28957-04-2 ]
  • [ 3400-45-1 ]
  • C26H36O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
37% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 10
  • [ 28957-04-2 ]
  • [ 98-89-5 ]
  • C27H38O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
34% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 11
  • [ 28957-04-2 ]
  • [ 828-51-3 ]
  • C31H42O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
22% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 12
  • [ 28957-04-2 ]
  • [ 455-24-3 ]
  • C28H31F3O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
22% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 13
  • [ 28957-04-2 ]
  • [ 456-22-4 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 4-fluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
59% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 14
  • [ 28957-04-2 ]
  • [ 455-38-9 ]
  • C27H31FO7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 15
  • [ 28957-04-2 ]
  • [ 445-29-4 ]
  • C27H31FO7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
27% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 16
  • [ 86-87-3 ]
  • [ 28957-04-2 ]
  • C32H36O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 17
  • [ 1477-50-5 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
47% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 18
  • [ 28957-04-2 ]
  • [ 1201-31-6 ]
  • C27H28F4O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
28% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 13 (72 mg, 0.2 mmol) was synthesized from 1 by oxidation with Jones Reagent andno further purification was needed for the next step [14]. Compound 1 or 13 (72 mg, 0.2 mmol) wasdissolved in 10 mL of dichloromethane and mixed with corresponding acid (0.24 mmol), EDCI andDMAP. The reaction was stirred at room temperature and monitored by TLC. After 6-8 h, the mixturewas poured into 10 mL of 10% HCl, and then extracted with DCM three times (each 10 mL). The organiclayer was combined, washed with water and saturated brine, sequentially, then dried over anhydrousNa2SO4, and concentrated in vacuo. The crude product was purified by column chromatography(MeOH/DCM 1:150 v/v) to give the target compounds 2-12 and 14-24.
  • 19
  • [ 28957-04-2 ]
  • 4-((5-methoxy-1-methyl-4,7-dioxo-4,7-dihydro-1H-indol-3-yl)methoxy)-4-oxobutanoic acid [ No CAS ]
  • ent-1α,6β,7α-trihydroxy-{14β-O-[((5-methoxy-1-methyl-4,7-dioxo-4,7-dihydro-1H-indol)-3-methoxyacyl)-propionyloxy]-15-oxo-7,20-epoxy-16-kaurene [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; Compound 10 (50 mg, 0.14 mmol) was dissolved in dichloromethane, then 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 36 mg, 0.19 mmol), catalytic amount of DMAP and 28a (48 mg, 0.15 mmol) were added. The reaction mixture was stirred at room temperature for about 2 h. Then the mixture was washed with 10 % HCl. The organic layer was washed with brine, dried over anhydrous Na2SO4. After flash chromatography (MeOH/CH2Cl2 1:300, v/v), 29a was obtained as white solid (70 mg, 76%). 1H NMR (300 MHz, CDCl3): delta (ppm) 5.99 (s, 1H), 5.94-5.80 (m, 4H), 5.59 (s, 4H), 5.12 (s, 2H), 4.41 (d, J = 5.1 Hz, 1H), 4.06 (d, J = 10.1 Hz, 1H), 3.88 (s, 3H), 3.82 (d, J = 10.4 Hz, 1H), 3.77 (s, 3H), 3.56-3.45 (m, 1H), 2.97-2.90 (m, 1H), 2.42 (d, J = 5.6 Hz, 2H), 1.31-1.15 (m, J = 14.8 Hz, 6H), 1.14-1.08 (m, 1H), 0.99 (d, J = 3.5 Hz, 6H); 13C NMR (75MHz, CDCl3): delta (ppm) 206.47, 171.87, 170.88, 162.09, 149.85, 129.64, 120.35, 106.77, 96.07, 76.21, 74.27, 73.44, 63.36, 59.55, 58.45, 56.53, 54.66, 41.31, 38.65, 33.72, 32.59, 30.49, 30.00, 29.57, 28.88, 21.71, 19.85; MS (ESI) m/z: 668.3 [M+H]+; HR-MS (ESI) m/z: calcd for C35H42NO12 [M+H]+ 668.2702, found 668.2713.
  • 20
  • [ 28957-04-2 ]
  • 5-((5-methoxy-1-methyl-4,7-dioxo-4,7-dihydro-1H-indol-3-yl)methoxy)-5-oxopentanoic acid [ No CAS ]
  • ent-1α,6β,7α-trihydroxy-{14β-O-[((5-methoxy-1-methyl-4,7-dioxo-4,7-dihydro-1H-indol)-3-methoxyacyl)-butyryl]-15-oxo-7,20-epoxy-16-kaurene [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; General procedure: Compound 10 (50 mg, 0.14 mmol) was dissolved in dichloromethane, then 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 36 mg, 0.19 mmol), catalytic amount of DMAP and 28a (48 mg, 0.15 mmol) were added. The reaction mixture was stirred at room temperature for about 2 h. Then the mixture was washed with 10 % HCl. The organic layer was washed with brine, dried over anhydrous Na2SO4. After flash chromatography (MeOH/CH2Cl2 1:300, v/v), 29a was obtained as white solid (70 mg, 76%).
  • 21
  • [ 127-88-8 ]
  • [ 28957-04-2 ]
  • [ 124-40-3 ]
  • C26H41Cl2N2O7P [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% Under nitrogen, at -78 C,6.0 mL (6.0 mmol) of LiN (TMS) 2 was added to 1.97 g (5.0 mmol)<strong>[28957-04-2]Oridonin</strong> in THF solution,After stirring for 5 min,1.55 g (6.0 mmol)Nitrogen mustard phosphorus dichloride, incubated for 1h,Warmed to -20 C,Add 10mL dimethylamine solution, incubated for 1h,Dilute hydrochloric acid pH6, ethyl acetate extraction, concentration,Ia white solid, yield 45%.
  • 22
  • [ 28957-04-2 ]
  • [ 15761-38-3 ]
  • N-Boc-L-alanine-(14-oridonin) ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With dicyclohexyl-carbodiimide; In dichloromethane; at 0 - 20℃; for 5.5h; 150 g (0.41 mol) of oridin (II) and 195 g (1.04 mol) of BOC-L-Ala were suspended in 1.35 kg of methylene chloride and cooled in an ice bath to 0 to 5 C. 213 g (1.04 mol)Dicyclohexylcarbodiimide (DCC), stirred for 0.5h after removing the ice bath, stirred at room temperature for 5h,TLC confirmed the complete reaction of starting material (methylene chloride: methanol = 10: 1, starting material Rf = 0.4, product Rf = 0.6).The reaction mixture was cooled to 0 C and allowed to stand for 2h, filtered and the filter cake washed with dichloromethane (300g x 3). The combined organic layers were concentrated to a white solid.Flash column chromatography on silica gel (methylene chloride: methanol = 100: 1 to 60: 1; v / v) collected the product fractions and concentrated to dryness under reduced pressure to about 140-165 g as a white solid powder.The above white powder was added 600g isopropyl ether, stirring beating washing 2h, filtration, the filter cake was washed with isopropyl ether (60g), at 25 under blast drying 4h, white powder 110 ~ 137g, yield 50 ~ 62% . (HPLC> 98%).
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 8h; General procedure: 3 (50 mg, 0.14 mmol), EDCI (61 mg, 0.32 mmol) and DMAP(8 mg, 0.5 mmol) were into anhydrous DCM (5 mL) and stirred at rtfor 15 min. N-Boc-glycine (40 mg, 0.23 mmol) was added and stirredfor another 8 h. After completion of the reaction as indicated byTLC, the reaction mixture was poured into H2O (10 mL) andextracted (DCM, 10 mL 3). The organic phases were combined,washed (H2O and brine), dried (anhydrous Na2SO4) and concentrated. Flash column chromatography (petroleum ether/acetone7:1 v/v) was used to get 4. Compounds 5-13 were prepared usingthe similar procedures.
  • 23
  • [ 28957-04-2 ]
  • [ 193954-28-8 ]
  • C45H49NO9 [ No CAS ]
  • 24
  • [ 28957-04-2 ]
  • [ 1038240-94-6 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(2-fluorophenyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 25
  • [ 28957-04-2 ]
  • [ 113934-32-0 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(4-chlorophenyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 26
  • [ 28957-04-2 ]
  • [ 113934-31-9 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(p-tolyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 27
  • [ 28957-04-2 ]
  • [ 4916-13-6 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(4-methoxyphenyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 28
  • [ 28957-04-2 ]
  • 1-(3,4-dimethoxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(3,4-dimethoxyphenyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 29
  • [ 28957-04-2 ]
  • 1-(3,4,5-trimethoxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-(3,4,5-trimethoxyphenyl)-1H-1,2,3-triazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 30
  • [ 10517-21-2 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 5-chloro-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 31
  • [ 4382-54-1 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 5-methoxy-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 32
  • [ 3093-97-8 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 6-fluoro-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of oridonin (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 33
  • [ 16732-65-3 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 6-bromo-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of oridonin (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 34
  • [ 16732-73-3 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 6-methoxy-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of oridonin (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 35
  • [ 28957-04-2 ]
  • [ 88210-96-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 5,6-dimethoxy-1H-indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 36
  • [ 32387-21-6 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1-methyl-1H-indole-3-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of <strong>[28957-04-2]oridonin</strong> (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 37
  • [ 486-73-7 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl isoquinoline-1-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of oridonin (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 38
  • [ 28957-04-2 ]
  • [ 675606-20-9 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7- oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 1H-indole-3-carboxylate [ No CAS ]
  • 39
  • [ 28957-04-2 ]
  • [ 675606-20-9 ]
  • C34H41NO9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: To a solution of oridonin (36.4mg, 0.1mmol) in 10mL dry CH2Cl2 and different carboxyl compounds (0.15mmol), the solution was treated with EDCI (0.3mmol) and 4-dimethylaminopyridine (DMAP) (10mg). The mixture was stirred at 25C for 2-8h and monitored by TLC. After completion of the reaction, water was added and the mixture was extracted with dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution and brine, and dried over Na2SO4. The evaporation of the solvents gave the crude products, which were purified by silica gel column (CH2Cl2/MeOH, 100:1) to afford compounds A1-9, B1-3, C1-9, D1, E, F.
  • 40
  • [ 28957-04-2 ]
  • C22H18FNO5 [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(3-(benzyloxy)-4-methoxybenzamido)-4-fluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 41
  • [ 28957-04-2 ]
  • [ 943-89-5 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl (E)-3-(4-methoxyphenyl)acrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid: mp 234.6-236.1 C; 1H NMR(500 MHz, CDCl3) delta 7.59 (d, J = 15.9 Hz, 1H), 7.43 (d, J = 8.7 Hz, 2H),6.88 (d, J = 8.7 Hz, 2H), 6.20(d, J = 15.9 Hz, 1H), 6.16(s, 1H), 5.92 (s,1H), 5.49 (s, 1H), 4.74 (s, 1H), 4.33 (d, J = 10.4 Hz, 1H), 4.08 (d,J = 10.4 Hz, 1H), 3.82 (s, 3H), 3.79 (d, J = 6.6 Hz, 1H), 3.50 (dd,J = 11.2, 5.7 Hz, 1H), 3.27 (d, J = 9.8 Hz, 1H), 2.65 (dt, J = 14.1, 9.1 Hz,1H), 2.33 (ddd, J = 27.5, 13.2, 8.3 Hz, 1H), 2.01 (dd, J = 12.8, 5.8 Hz,1H), 1.79-1.71 (m, 1H), 1.71-1.64 (m, 1H), 1.64-1.55 (m, 2H),1.50-1.44 (m, 1H), 1.33-1.22 (m, 3H), 1.12 (s, 6H), 0.87 (dd, J = 13.3,6.5 Hz, 1H).13C NMR (126 MHz, CDCl3) delta 206.71, 165.45, 161.84,149.84, 146.35, 130.08, 126.51, 120.20, 114.40, 113.97, 96.22, 73.64,73.31, 63.39, 61.79, 59.87, 55.39, 54.55, 41.32, 41.24, 38.63, 33.75,32.51, 30.48, 29.97, 21.59, 19.73. HRESIMS m/z 525.2487 [M+H]+(calcd for C30H37O8 525.2483).
  • 42
  • [ 28957-04-2 ]
  • [ 20329-98-0 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl (E)-3-(3,4,5-trimethoxyphenyl)acrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 43
  • [ 28957-04-2 ]
  • [ 14737-89-4 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl (E)-3-(3,4-dimethoxyphenyl)acrylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 44
  • [ 28957-04-2 ]
  • [ 1929-29-9 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(4-methoxyphenyl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 45
  • [ 28957-04-2 ]
  • [ 2107-70-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(3,4-dimethoxyphenyl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 46
  • [ 25173-72-2 ]
  • [ 28957-04-2 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(3,4,5-trimethoxyphenyl)propanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: Oridonin (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 47
  • [ 28957-04-2 ]
  • C16H11F4NO4 [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 4-fluoro-3-(4-(trifluoromethoxy)benzamido)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 48
  • [ 28957-04-2 ]
  • 3-(3,4-dimethoxybenzamido)-4-fluorobenzoic acid [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(3,4-dimethoxybenzamido)-4-fluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 49
  • [ 2942-59-8 ]
  • [ 28957-04-2 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 2-chloronicotinate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 50
  • [ 28957-04-2 ]
  • [ 1077-28-7 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 5-(1,2-dithiolan-3-yl)pentanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 51
  • [ 28957-04-2 ]
  • [ 2991-28-8 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 2,5-difluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: Oridonin (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 52
  • [ 28957-04-2 ]
  • [ 114045-96-4 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 4-(benzyloxy)-2-fluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 53
  • [ 28957-04-2 ]
  • [ 61079-72-9 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 2,3,4-trifluorobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: Oridonin (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 54
  • [ 28957-04-2 ]
  • [ 619-65-8 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 4-cyanobenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 55
  • [ 28957-04-2 ]
  • [ 1642-81-5 ]
  • (1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 4-(chloromethyl)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: Oridonin (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 56
  • [ 28957-04-2 ]
  • [ 196404-55-4 ]
  • 3-(tert-butyl)-5-((1S,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl)(4S,5R)-2-(4-methoxyphenyl)-4-phenyloxazolidine-3,5-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: Oridonin (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 57
  • [ 28957-04-2 ]
  • C10H11BrO4 [ No CAS ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 3-(2-bromoethoxy)-4-methoxybenzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 58
  • [ 28957-04-2 ]
  • [ 951-82-6 ]
  • (1S,4aR,5S,6S,6aR,9S,11aS,11bS,14R)-1,5,6-trihydroxy-4,4-dimethyl-8-methylene-7-oxododecahydro-1H-6,11b-(epoxymethano)-6a,9-methanocyclohepta[a]naphthalen-14-yl 2-(3,4,5-trimethoxyphenyl)acetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; General procedure: <strong>[28957-04-2]Oridonin</strong> (100 mg, 0.27 mmol) wasmixed with 4-methoxycinnamic acid (48 mg, 0.27 mmol),EDCI(157 mg, 0.82 mmol) and DMAP(101 mg, 0.82 mmol) in drydichloromethane(10 mL) and stirred at room temperature overnight.The mixturewas poured into 1MHCl solution, and extractedwith dichloromethane. The organic layer was combined, washedwith water and saturated NaCl solutions, dried over anhydrousMgSO4, filtered, and concentrated in vacuo. The crude product waspurified by column chromatography to give the compound 20(122 mg, 86%) as a white solid
  • 59
  • [ 108-30-5 ]
  • [ 28957-04-2 ]
  • C24H32O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With dmap; triethylamine; In dichloromethane; at 20℃; for 7h; General procedure: Compounds 1, 2 or 5 (0.50mmol) were dissolved in 6mL anhydrous DCM in the presence of TEA (2.5mmol), DMAP (0.25mmol) and succinic anhydride or glutaric anhydride (1.0mmol) and stirred at room temperature for 6-8h. The mixture was extracted with DCM (3×20mL), washed with brine, dried over anhydrous Na2SO4, and evaporated in vacuo to yield intermediates 8a-c and 9a-c. Intermediates 10a-c or 15a-c (0.20mmol) were dissolved in anhydrous DCM and directly reacted with 7a-c (0.22mmol) under the condition of EDCI (0.60mmol) and DMAP (0.10mmol). After stirring overnight at room temperature, the reaction was quenched and extracted with DCM (3×20mL), washed with brine, dried over anhydrous Na2SO4, and evaporated in vacuo. Finally, H2S-releasing derivatives 10a-c, 11a-c, 12a-c, 13a-c, 14a-c and 15a-c were obtained by flash column chromatography (DCM/MeOH 100:1-200:1, v/v).
With dmap; triethylamine; In dichloromethane; at 20℃; for 6h; Dissolve 68mg ADT-OH (0.3mmol) in anhydrous acetone,Add 117 muL (0.9 mmol) 6-bromohexanol,125mg potassium carbonate (0.9mmol), reflux for 8h,After the reaction was completed, the insoluble material was removed by suction filtration, and the filtrate was spin-dried on silica gel column chromatography (petroleum ether: ethyl acetate=4:1) to obtain orange-red compound 2.Then 96mg <strong>[28957-04-2]Oridonin</strong> 3 (0.25mmol) was dissolved in 6ml of anhydrous dichloromethane,Add 50mg succinic anhydride (0.50mmol),173muL triethylamine (1.25mmol), catalytic amount of DMAP,Stir at room temperature for 6h.TLC monitors the reaction and stops the reaction when the reaction is complete or does not continue.Separate the liquid after washing and wash twice with saturated saline.It was dried over anhydrous sodium sulfate, filtered and concentrated to obtain compound 4a.74.3 mg of compound 4a (0.16 mmol) was dissolved in anhydrous dichloromethane,Add 92mg EDCI (0.48mmol),A catalytic amount of DMAP and 52 mg of compound 2 (0.16 mmol) were stirred at room temperature overnight.The reaction was monitored by TLC. After the reaction was completed, about 20 mL of water was added and extracted three times with dichloromethane, 10 mL each time.Combine the organic phases and wash twice with saturated brine,Dry over anhydrous sodium sulfate, filter and concentrate,Silica gel column chromatography (dichloromethane: methanol=300:1) gave the orange-red target derivative 5a with a yield of 40.2%.
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