Chiral diaryl-beta-lactam compound, preparation method and pharmaceutical application thereof
A technology of lactams and compounds, applied in medicines, the field of novel chiral diaryl-β-lactam compounds, can solve the problems of prolonging the survival period of patients, toxic and side effects, etc.
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Embodiment 1
[0044] Example 1 (3S,4R)-1-(3,4,5-trimethoxyphenyl)-3-aminomethyl-4-(3-hydroxyl-4-methoxyphenyl)azetidine Synthesis of alkan-2-ones (1)
[0045] Referring to the literature (J.Med.Chem.2016,59,10329-10334) method, the present invention synthesizes the target compound 1 according to the following route:
[0046]
[0047] Reagents and conditions: (a) Pd 2 (dba) 3 (1%),(R,R,R)-Ph-SKP(2.5%),K 2 CO 3 (aq.), CH 2 Cl 2 ,25℃, 3h; (b)Sn[N(TMS) 2 ] 2 , toluene, reflux, 3h; (c) TBAF, THF, 0℃, 1h; (d) i) BnCl, K 2 CO 3 , MeCN, reflux, 12h; ii) B 2 (pin) 2 (1.3equiv), CuCl(5%), MeOH(1.5equiv), PPh 3 (15%),t-BuOLi(10%),THF,25℃,12h; iii)NaBO 3 4H 2 O,H 2 O, THF, 25℃, 2 h; (e) Isoindoline-1,3-dione, DIAD, PPh 3 , THF, 25℃, 3h; (f) N 2 h 4 .H 2 O, EtOH, reflux, 4h; (g) Pd / C, H 2 , EtOH, 25°C, 12h.
[0048] 1.1(S)-2-[1-(3-tert-butyldimethylsilyloxy-4-methoxyphenyl)-1-(3,4,5-trimethoxyphenylamino)methyl ] Synthesis of ethyl acrylate (1c)
[0049] Into a 50 mL Schlenk tu...
Embodiment 2
[0062] The synthesis of embodiment 2 compound 2,3,4,5,6,7,8 and 9
[0063]
[0064] The specific operation is as follows: In a 25mL eggplant-shaped bottle, weigh the raw material for 1h (20mg, 0.04mmol), dissolve it in 1.5mL of dichloromethane, add acid chloride (0.21mmol) and triethylamine (25μL, 0.21mmol), and stir at room temperature , TLC spot plate detection reaction progress. After the reaction was complete, water was added, extracted three times with dichloromethane, the combined organic phases were washed once with saturated brine, and dried over anhydrous sodium sulfate. After filtration and concentration by rotary evaporation, 10% Pd / C (3 mg) and ethanol (1 mL) were added, and the reaction was carried out at room temperature under normal pressure hydrogen for 12 hours. Remove Pd / C by filtration, evaporate to dryness, and separate and purify with silica gel (300-400 mesh) column chromatography.
[0065] 2.1(3S,4R)-1-(3,4,5-trimethoxyphenyl)-4-(3-hydroxy-4-methoxy...
Embodiment 3
[0089] Example 3 (3S,4R)-1-(3,4,5-trimethoxyphenyl)-4-(3-hydroxyl-4-methoxyphenyl)-3-phthalimide Synthesis of Methylazetidin-2-one (10)
[0090]
[0091] In a 25mL eggplant-shaped flask, 1g (20mg, 0.032mmol), Pd / C (3mg) and ethanol (1mL) were added. Reacted at room temperature under normal pressure with hydrogen for 12 hours, filtered to remove the catalyst, and separated by column chromatography (developer: PE / EA 2:1) to obtain 14 mg of yellow solid (10) with a yield of 83%. mp 88-90℃. 1 HNMR (400MHz, CDCl 3 ):δ7.87-7.85(m,2H),7.74-7.72(m,2H),6.84(s,1H),6.79(d,J=8.2Hz,1H),6.73(d,J=8.2Hz, 1H), 6.52(s, 2H), 5.66(s, 1H), 4.97(s, 1H), 4.27(dd, J=14.2, 4.8Hz, 1H), 4.11(dd, J=13.8, 9.8Hz, 1H ),3.82(s,3H),3.75(s,3H),3.70(s,6H),3.44-3.41(m,1H). 13 C NMR (150MHz, CDCl 3): δ167.4, 163.1, 152.8, 146.2, 145.6, 133.9, 133.6, 132.9, 131.2, 129.6, 122.9, 117.1, 111.3, 110.4, 94.3, 60.3, 59.5, 58.4, 55.4, 55.3, 35.9.ESI z):519.1(M+H + ).ESI-HRMS(m / z):calcd for C 28 h 27 N 2 o ...
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