4Hz, 1H),4. 51 - 4. 44 (m, 2H),4. 29 (d,J= 3. 2Hz, 1H),4. 19 (d,J =6. 6Hz, 1H),3. 69 (s, 1H),3. 66 (t,J= 6. 4Hz, 1H),3. 55 - 3. 45 (m, 4H) ,3.44- 3. 37(m, 2H), 3. 04(dd,J= 15. 8, 6. 3Hz, 1H), 2. 67 (dd,J= 15. 8, 12. 0Hz, 1H), 2. 29- 2. 25 (m, 1H), 2. 18 - 2. 12 (m, 1H),I. 84 -I. 77 (m, 2H),I. 73 -I. 66 (m, 4H),I. 60 (d,J= 12. 6Hz, 1H),L54 -I. 47 (m, 1H),L36 -I. 24 (m, 5H),I. 02 (s, 3H),0. 85 (s, 3H).
[0064] 實施例3 :去氫表雄酮糖基化衍生物的制備
[0067] 【式（A-4-2)所示化合物】將A-3 (889mg,I. 2mmol)、CH12 (200mg, 0? 6mmol)溶 解在無水二氯甲烷（20mL)中，加入三氟甲磺酸三甲基硅脂（0. 24mL，0. 3mmol)，室溫反 應(yīng)6小時。反應(yīng)完全后，減壓除去溶劑，加入水（30mL)，乙酸乙酯（30mLX3)萃取，合并 有機(jī)相，無水硫酸鈉干燥，硅膠柱層析（PE:EA= 3 :1)純化，得到如式（A-4-2)所示的白 色固體（415mg，76 %))。1HNMR(400MHz，CDC13)S8.01(d，J= 8.2Hz，2H)，7.97(d，J= 8. 2Hz, 2H), 7. 90 (d,J= 8. 2Hz, 2H), 7. 83 (d,J= 8. 2Hz, 2H), 7. 55 - 7. 48 (m, 3H), 7. 40 (dd,J =16. 9, 9. 2Hz, 5H), 7. 34(t,J= 7. 7Hz, 2H),7. 29 (t,J= 7. 7Hz, 2H),5. 90 (t,J= 9. 6Hz, 1H), 5. 64(t,J= 9. 7Hz, 1H), 5. 50 (dd,J= 9. 3, 8. 3Hz, 1H), 5. 26 (d,J= 4. 5Hz, 1H), 4. 95 (d,J= 7. 8Hz, 1H), 4. 62 - 4. 57 (m, 2H), 4. 18 - 4. 15 (m, 1H), 3. 59 - 3. 49 (m, 1H), 3. 02 (dd,J= 15. 5, 6. 3Hz, 1H), 2. 61 (dd,J= 15. 4, 12. 0Hz, 1H), 2. 48 (d,J =12. 5Hz, 1H),2. 23 - 2. 17m, 3H),2. 08 - 2. 00 (m, 1H),L96 (d,J= 12. 4Hz, 1H),L92-1. 85 (m, 1H),L11 (s, 3H),0. 99 (s, 3H).
[0068] 【式（B-4-2)所示化合物】按照化合物A-4-2的合成方法以化合物B-3和CH12 為原料，得到如式（B-4-2)所示的白色固體（73%)。 111匪1?(4001抱，〇)(：13)58.11-8. 04 (m, 4H),8. 00 - 7. 95 (m, 2H),7. 51 (t, J = 7. 4Hz, 1H),7. 45 - 7. 35 (m, 7H),7. 26 (dd, J =4. 8, 2. 7Hz, 2H), 6. 05(t, J = 10. 0Hz, 1H),5. 64 (dd, J = 3. 2, I. 8Hz, 1H),5. 25 (d, J = 1.4Hz，lH)，4.70(dd，J=11.8,2.1Hz，lH)，4.69 - 4.66 (m，lH)，4.54- 4. 51 (m, 1H), 4. 47 (dd,J= 11. 9, 5. 1Hz, 1H), 3. 74 - 3. 65 (m, 1H), 3. 03 (dd,J= 15. 5, 6. 3Hz, 1H), 2. 61 (dd,J= 15. 5, 12. 0Hz, 1H) , 2. 48 - 2. 40 (m, 1H), 2. 23 - 2. 17 (m, 1H),I. 96 (d,J= 10. 5Hz, 1H),L60 -I. 49 (m, 3H),L36 -I. 21 (m, 4H),I. 10 (s, 3H) ,0. 93 (s, 3H).
[0069] 【式（C-4-2)所示化合物】按照化合物A-4-2的合成方法以化合物C-3和CH12 為原料，得到如式（C-4-2)所示的白色固體（78%)。1HNMR(400MHz，CDC13) 5 8. 10(dd,J =8. 3,I. 2Hz, 2H), 7. 98 (dd,J= 8. 3,I. 2Hz, 2H), 7. 82 (dd,J= 8. 3,I. 2Hz, 2H), 7. 64 -7. 59 (m, 1H), 7. 55 - 7. 47 (m, 3H), 7. 45 - 7. 36 (m, 3H), 7. 28 - 7. 24 (m, 3H), 5. 86 (dd,J =10.I, 3. 4Hz, 1H), 5. 67(t,J= 10. 0Hz, 1H), 5. 61 (dd,J= 3. 4,I. 8Hz, 1H), 5. 45- 5. 39 (m, 1H), 5. 17 (t,J= 4. 3Hz, 1H), 4. 31 - 4. 23 (m, 1H), 3. 66 - 3. 55 (m, 1H), 3. 11 - 3. 00 (m, 1H), 2. 65 (dd,J= 15. 5, 11. 9Hz, 1H), 2. 54 - 2. 43 (m, 2H), 2. 39 (dd,J= 17. 8, 6. 7Hz, 1H), 2. 27 - 2. 21 (m, 1H), 2. 14 - 2. 43 (m, 1H), 2. 04 -I. 92 (m, 3H),I. 86 -I. 69 (m, 5H),I. 35 (d,J= 6. 3Hz, 3H),I. 16 (s, 3H),I. 15 (s, 3H).
[0070] 【式（D-4-2)所示化合物】按照化合物A-4-2的合成方法以化合物D-3和 CH12為原料，得到如式（D-4-2)所示的白色固體（72 %)。1HNMR(400MHz,CDCl3) 8 8. 11 (d,J= 7. 3Hz, 2H), 8. 03(d,J= 7. 2Hz, 2H), 7. 97 (d,J= 7. 3Hz, 2H), 7. 79 (d,J =7. 3Hz, 2H), 7. 62 (t,J= 7. 4Hz, 1H), 7. 56 (dd,J= 13.I, 5. 7Hz, 1H), 7. 53-7. 46 (m, 3H), 7. 44 - 7. 38 (m, 5H), 7. 27 - 7. 22 (m, 2H), 5. 98 (d,J= 2. 9Hz, 1H), 5. 78 (dd,J =10. 3, 8. 0Hz, 1H), 5. 60(dd,J= 10. 4, 3. 4Hz, 1H), 5. 26 (d,J= 4. 4Hz, 1H), 4. 92 (d,J =8.0Hz, 1H), 4.69 (dd,J= 11. 2,6.9Hz, 1H), 4.42 (dd,J= 11. 2,6.5Hz, 1H), 4.33 (t,J =6. 7Hz, 1H), 3. 62 - 3. 52 (m, 1H), 3. 02 (dd,J= 15. 5, 6. 3Hz, 1H), 2. 61 (dd,J= 15. 5, 12. 0Hz, 1H), 2. 48 (d,J= 12. 5Hz, 1H), 2. 26 - 2. 16 (m, 3H), 2. 08 -I. 98 (m, 2H),L93 - 1. 86 (m, 1H),I. 81 -I. 78 (m, 2H),I. 76 -I. 59 (m, 5H),I. 11 (s, 3H),I. 01 (s, 3H).
[0071] 【式（A-5-2)所示化合物】將A-4-2 (400mg, 0? 44mmol)溶解在無水四氫呋 喃（IOmL)和甲醇（IOmL)混合溶劑中，加入甲醇鈉（475mg, 8. 8mmol)，室溫反應(yīng)6小 時。反應(yīng)完全后，除去溶劑，加入稀鹽酸調(diào)pH呈弱酸性，乙酸乙酯（30mLX3)萃取，無 水硫酸鈉干燥，硅膠柱層析（DCM:MeOH= 5 :1)分離純化，得到如式（A-5-2)所示的白 色固體（178mg，83 %)。1HNMR(400MHz，DMS0-d6)S5.95 (d，J= 3.2Hz，1H) ,5. 38 (d，J =3. 3Hz, 1H), 4. 94 (d,J= 4. 6Hz, 1H), 4. 92 - 4. 88 (m, 1H), 4. 45 (s, 1H), 4. 23 (d,J =7. 7Hz, 1H), 3. 64(dd,J= 11. 2, 5. 4Hz, 1H), 3. 52 - 3. 45 (m, 1H), 3. 42 (dd,J= 9. 8, 3. 8Hz, 1H), 3. 18 - 3. 11 (m, 1H), 3. 05 (d,J= 4. 7Hz, 3H), 2. 93 - 2. 88 (m, 1H), 2. 70 (dd,J =15. 6, 12. 0Hz, 1H),2. 41(dd,J= 13. 0, 3. 3Hz, 1H), 2. 31 (d,J= 11. 2Hz, 1H), 2. 23- 2. 12 (m, 2H), 2. 09 - 2. 01 (m, 1H),I. 05 (s, 6H).
[0072] 【式（B-5-2)所示化合物】按照化合物A-5-2的合成方法以化合物B-4-2為原 料，得到如式（B-5-2)所示的白色固體（85 %)。1HNMR(400MHz,DMS0-d6)S5. 35 (dd,J =11.I, 8. 3Hz, 1H), 4. 78 (d,J=I. 2Hz, 1H), 4. 69 (d,J= 5. 0Hz, 1H), 4. 66 (d,J =4. 3Hz, 1H), 4. 53 (d,J= 5. 9Hz, 1H), 4. 43 (t,J= 5. 9Hz, 1H), 3. 65 (dd,J= 10. 3, 6. 2Hz, 1H), 3. 56 (s, 1H), 3. 49 - 3. 39 (m, 4H), 3. 40 - 3. 35 (m, 2H), 3. 17 (d,J= 5. 2Hz, 1H), 3. 08(dd, J = 15. 8, 6. 4Hz, 1H), 2. 71 (dd, J = 15. 8, 11. 9Hz, 1H), 2. 41-2. 36 (m, 1H), 2. 35 - 2. 30 (m, 1H), 2. 25 (d, J = 11. 3, 1H), 2. 22 - 2. 15 (m, 1H), 2. 09 - 2. 02 (m, 1H), I. 91 - I. 82 (m, 3H), I. 75 - I. 67 (m, 4H), I. 41 - I. 33 (m, 1H), I. 06 (d, J = 1. 6Hz, 1H).
[0073]【式（C-5-2)所示化合物】按照化合物A-5-2的合成方法以化合物C-4-2 為原料，得到如式（C-5-2)所示的白色固體（94 % )。1H NMR (400MHz, CDCl3) 8 5. 38 (s, 1H), 4. 97 (s, 1H), 3. 96 (d, J = 36. 0Hz, 2H), 3. 78 - 3. 73 (m, 1H) ,3.57- 3. 52 (m, 1H), 3. 50 - 3. 45 (m, 1H), 3. 02 (dd, J = 15. 4, 6. 2Hz, 1H), 2. 62 (dd, J = 15. 4, 12. 0Hz, 1H), 2. 48 (d, J = 12. 2Hz, 1H), 2. 38 (d, J = 10. 5Hz, 1H), 2. 24- 2. 18 (m, 2H), 2. 14 - 2. 04 (m, 1H), I. 97 - I. 85 (m, 3H), I. 84 - I. 68 (m, 4H),