一种铱催化氢化合成3-哌啶酮衍生物的方法_2

文档序号:9919213阅读:来源:国知局
即可分 离得到纯的产物3-哌啶酮3,反应式及配体如下:
[0039]
[0040] l-Benzyl-2-phenylpiperidin-3-〇ne(3a):known compound, White solid,93 % yield,Rf=0.70(petroleum ether/EtOAc 5/l),mp 129-130 °C. 4 NMR(400MHz,CDC13) δ 7. 48-7. 19 (m, 11H) , 3. 93 (s, 1H) , 3. 78 (d, J = 1 3. 6Hz, 1H) , 3. 2 1 (d, J = 13. 6Hz, 1H), 3. 12 (dt, J = 12. 1, 4. 5Hz, 1H), 2. 69 (dt, J = 14. 8, 6. 1Hz, 1H), 2. 50-2. 32 (m, 2 H), 2. 11-1. 92(m, 2H) ;13C NMR(100MHz, CDC13) δ 208. 0, 138. 5, 137. 6, 128. 7, 128. 6, 128. 6, 128. 3, 127. 9, 127. 1, 77. 8, 59. 3, 49. Ο, 38. 1, 23. 4.
[0041 ] l-Benzyl-2-〇-tolylpiperidin_3-〇ne(3b):unknown compound, colorless oil,96 % yield,Rf= 0.70(petroleum ether/EtOAc 5/1). 4 NMR(400MHz,CDC13) δ7· 53-7. 43 (m, 1H), 7. 32-7. 11 (m, 8H), 4. 05 (s, 1H), 3. 72 (d, J = 13. 5Hz, 1H), 3. 12 (dd, J = 9. 0, 2. 9Hz, 1H), 3. 04 (d, J = 13. 5Hz, 1H), 2. 71 (ddd, J = 8. 3, 7. 2, 4. 3Hz, 1H), 2. 47-2. 27 (m ,5H),2.13-1.97(m,lH),1.97-1.86(m,lH) ;13C NMR(100MHz,CDC13) δ 206·8,138·6,137·5, 136. 2, 130. 9, 129. 5, 128. 7, 128. 3, 127. 7, 127. 0, 126. 0, 76. 2, 59. 7, 50. 4, 38. 7, 23. 1, 20. 2
[0042] l-Benzyl-2-m-tolylpiperidin-3-〇ne (3c) : unknown compound, white solid, 93 % yield, Rf= 0. 70 (petroleum ether/EtOAc 5/1), mp 86-87 °C . :Η NMR(400MHz,CDC13) δ 7. 34-7. 17 (m, 8H),7. 10 (dd, J = 7. 6, 4. 1Hz, 1H),3. 88 (s, 1H),3. 78 ( d, J = 13. 6Hz, 1H), 3. 19 (d, J = 13. 6Hz, 1H), 3. 11 (dt, J = 12. 2, 4. 6Hz, 1H), 2. 68 (dt, J = 14.9,6.1Hz,lH),2.46-2.30(m,5H),2.09-1.91(m,2H) ;13C NMR(100MHz,CDC13) δ 208·2,13 8. 5, 138. 2, 137. 5, 129. 4, 128. 7, 128. 7, 128. 5, 128. 3, 127. 1, 125. 7, 77. 8, 59. 3, 49. 0, 38. 1 ,23. 4, 21. 5.
[0043] l-Benzyl-2-p-tolylpiperidin-3-〇ne (3d) : unknown compound, white solid, 91 % yield, Rf= 0. 70 (petroleum ether/EtOAc 5/1), mp 107-108 °C . :Η NMR (400MHz, CDC13) δ 7. 36-7. 13 (m, 9H),3. 88 (s, 1H),3. 78 (d, J = 13. 6Hz, 1H),3. 18 (d, J = 13. 6Hz, 1H), 3. 10 (dt, J = 12. 1, 4. 5Hz, 1H), 2. 68 (dt, J = 14. 9, 6. 0Hz, 1H), 2. 46-2. 29 (m, 5 H), 2. 07-1. 90(m, 2H) ;13C NMR(100MHz, CDC13) δ 208. 1,138. 6, 137. 6, 134. 5, 129. 4, 128. 6, 128. 62, 128. 3, 127. 1, 77. 6, 59. 3, 49. 2, 38. 2, 23. 4, 21. 2.
[0044] l-Benzyl-2 -(3,5-dimethylphenyl)piperidin_3-〇ne(3e) : unknown compound, yellow solid, 85 % yield,Rf= 0. 70(petroleum ether/EtOAc 5/1), mp 74-751:.? NMR (400MHz,CDC13) δ 7. 36-7. 18 (m,5H) ,7.04 (s,2H) ,6.92 (s,1H) ,3.92-3. 71( m, 2H), 3. 18 (d, J = 13. 6Hz, 1H), 3. 11 (dt, J = 12. 0, 4. 6Hz, 1H), 2. 77-2. 62 (m, 1H), 2. 47-2. 25(m,8H),2.11-1.88(m,2H) ;13C NMR(100MHz,CDC13) δ 208·3,138·7,138·0,137·4,129·7, 128. 7, 128. 3, 127. 0, 126. 5, 77. 8, 59. 3, 49. 0, 38. 0, 23. 3, 21. 4.
[0045] 1-B en z y 1-2 - (3-me t ho xyph eny 1) p i p er i d i n_3-on e (3 f) : unkno wn compound, colorless oil, 88 % yield, Rf= 0.60 (petro 1 eum ether/EtOAc 5/1).4^^(40010^,00(:13)5 7.34-7.17(111,611),7.01(11 = 5.1^,211),6.89-6. 79 (m, 1H), 3. 90 (s, 1H), 3. 85-3. 75 (m, 4H), 3. 21 (d, J = 13. 6Hz, 1H), 3. 11 (dt, J = 12. 2, 4. 6Hz, 1H), 2. 68 (dt, J = 14. 8, 6. 1Hz, 1H), 2. 47-2. 30 (m, 2H), 2. 09-1. 91 (m, 2H) ;13C NMR(100MHz,CDC13)S 207.9,159.9,139.2,138.5,129.6,128.6,128.3,127.1,121.1,114. 2, 113. 4, 77. 6, 59. 3, 55. 2, 49. 0, 38. 1, 23. 4.
[0046] l-Benzyl-2 -(4-(benzyloxy) phenyl) piperidin-3-〇ne(3g) : unknown compound, colorless oil,88 % yield, Rf= 0. 50(petroleum ether/EtOAc 5/1). :Η NMR (400MHz, CDC13) δ 7. 45-7. 17 (m, 12H),7. 00-6. 94 (m, 2H),5. 03 (s, 2H),3. 85 (s, 1H),3. 7 8 (d, J = 13. 6Hz, 1H), 3. 16 (d, J = 13. 6Hz, 1H), 3. 09 (dt, J = 12. 0, 4. 4Hz, 1H), 2. 66 (dt, J =14. 8, 5. 9Hz, 1H), 2. 38 (tdd, J = 19. 2, 12. 9, 6. 4Hz, 2H), 2. 06-1. 88 (m, 2H) ;13C NMR(100MHz,CDC13) δ 208. 2, 158. 6, 138. 6, 137. 1,129. 9, 129. 9, 128. 7, 128. 6, 128. 3, υβ?, 127. 6, 127. 1, 115. 0, 77. 26, 70. 1, 59. 3, 49. 3, 38. 2, 23. 4·
[0047] l-Benzyl-2 - (4-fluorophenyl) piperidin-3-〇ne (3h) : unknown compound, yellow solid, 86 % yield,Rf= 0. 70(petroleum ether/EtOAc 5/1), mp 94-95 °C · 4 NMR (400MHz,CDC13) δ 7. 44-7. 35 (m,2H),7. 33-7. 20 (m,5H),7. 06 (dd d,J = 10. 6, 5.9,2. 5Hz,2H) ,3.89 (s,lH) ,3.75 (d,J = 13.6Hz,1H) ,3.18 (d,J = 13. 6Hz, 1H), 3. 11 (dt, J = 12. 1, 4. 2Hz, 1H), 2. 66 (dt, J = 15. 0, 5. 5Hz, 1H), 2. 49 -2. 31 (m, 2H), 2. 10-1. 93 (m, 2H) ;13C NMR(100MHz, CDC13) δ 207. 5, 162. 5 (d, Jc F = 244. 7Hz), 138. 3, 133. 3 (d, Jc F= 3. 2Hz), 130. 3 (d, J c F= 7. 9Hz), 128. 6, 128. 3, 127. 2, 115 ? 5(d, Jc F= 21. 3Hz), 77. 1,59. 4, 49. 4, 38. 3, 23. 4 ; 19F NMR(376MHz, CDC13) δ -114. 53.
[0048] l-Benzyl-2 - (3-chlorophenyl) piperidin-3-〇ne (3i) : unknown compound, colorless oil,90 % yield, Rf= 0. 70(petroleum ether/EtOAc 5/1). :Η NMR(400MHz, CDC13) δ 7. 45 (s, 1H), 7. 37-7. 18 (m, 8H), 3
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