Supporting Information Organocatalytic Synthesis of 4-Aryl-1,2,3,4-tetrahydropyridines from Morita-Baylis-Hillman Carbonates through a One-Pot Three-Component Cyclization Jian Wei, Yuntong Li, Cheng Tao, Huifei Wang, Bin Cheng, Hongbin Zhai,*, and Yun Li*,, Email: liyun@lzu.edu.cn; zhaihb@pkusz.edu.cn The State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University, Shenzhen 518055, China State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China List of content 1. Separation Methods for Tetrahydropyridines 6a-x and Lactams 7a and 7b.. S1-S2 2. NMR spectra S3-S58 3. X-ray of compound 6hb, 6na, 7aa and 7bb.. S59-S60
1. Separation Methods for Tetrahydropyridines 6a-x and Lactams 7a and 7b 6a: 6aa and 6ab were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6b: 6ba and 6bb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6c: 6ca and 6cb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 65:35, flow rate: 2 ml/min). 6d: 6da and 6db were separated by HPLC (Waters sunfire silica, column size: 19 150 mm, 5 μm, EtOH/Hexane = 2:98, flow rate: 25 ml/min). 6e: 6ea and 6eb were separated by HPLC (Waters sunfire silica, column size: 19 150 mm, 5 μm, EtOH/ Hexane = 2:98, flow rate: 25 ml/min). 6f: 6fa and 6fb were separated by chiral SFC (ChomegaChiral CCC, column size: 20 mm I.D. 250mm, 5 μm, CO 2 (liquid)/meoh (0.1% NH 4 OH) = 80:20, flow rate: 60 g/min). 6g: 6ga and 6gb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6h: 6ha and 6hb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6i: 6ia and 6ib were separated by HPLC (Waters sunfire silica, column size: 19 150 mm, 5 μm, EtOH/ Hexane = 2:98, flow rate: 25 ml/min). 6j: 6ja and 6jb were separated by HPLC (Waters sunfire silica, column size: 19 150 mm, 5 μm, EtOH/ Hexane = 2:98, flow rate: 25 ml/min). 6k: 6ka and 6kb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 70:30, flow rate: 2 ml/min). 6l: 6la and 6lb were separated by HPLC (Waters sunfire C 18, column size: 19 150 mm, 5 μm, water (10 mm NH 4 HCO 3 )/CH 3 CN = 50:50, flow rate: 25 ml/min). 6m: 6ma and 6mb were separated by HPLC (Waters sunfire C 18, column size: 19 150 mm, 5 μm, water (10 mm NH 4 HCO 3 )/CH 3 CN = 50:50, flow rate: 25 ml/min). 6n: 6na and 6nb were separated by HPLC (Waters sunfire C 18, column size: 10 250 mm, 5 μm, water/ch 3 CN = 45:55, flow rate: 2 ml/min). 6o: 6oa and 6ob were separated by HPLC (Waters sunfire silica, column size: 19 150 mm, 5 μm, EtOH/ Hexane = 2:98, flow rate: 25 ml/min). 6p: 6pa and 6pb were separated by chiral SFC (ChomegaChiral CC4, column size: 20mm I.D. 250mm, 5 μm, CO 2 (liquid)/meoh (0.1% NH 4 OH) = 80/20, flow rate: 60 g/min). 6q: 6qa and 6qb were separated by chromatography on silica gel with elution of PE/EA = 20:1. 6r: 6ra and 6rb were separated by chromatography on silica gel with elution of PE/EA = 20:1. 6s: 6sa and 6sb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6t: 6ta and 6tb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 55:45, flow rate: 2 ml/min). 6u: 6ua and 6ub were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 45:55, flow rate: 2 ml/min). 6v: 6va and 6vb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 45:55, flow rate: 2 ml/min). S1
6w: 6wa and 6wb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 50:50, flow rate: 2 ml/min). 6x: 6xa and 6xb were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 45:55, flow rate: 2 ml/min). 7a: 7aa and 7ab were separated by HPLC (Waters sunfire C 18, column size: 10 150 mm, 10 μm, water/ch 3 CN = 30:70, flow rate: 2 ml/min). 7b: 7bb could be obtained by recrystallization. S2
2. NMR spectra Fig. S1. 1 H NMR of compound 6aa (400 MHz, CDCl 3 ). Fig. S2. 13 C NMR of compound 6aa (100 MHz, CDCl 3 ). S3
Fig. S3. 1 H NMR of compound 6ab (400 MHz, CDCl 3 ). Fig. S4. 13 C NMR of compound 6ab (100 MHz, CDCl 3 ). S4
Fig. S5. 1 H NMR of compound 6ba (400 MHz, CDCl 3 ). Fig. S6. 13 C NMR of compound 6ba (100 MHz, CDCl 3 ). S5
Fig. S7. 1 H NMR of compound 6bb (400 MHz, CDCl 3 ). Fig. S8. 13 C NMR of compound 6bb (100 MHz, CDCl 3 ). S6
Fig. S9. 1 H NMR of compound 6ca (400 MHz, CDCl 3 ). Fig. S10. 13 C NMR of compound 6ca (100 MHz, CDCl 3 ). S7
Fig. S11. 1 H NMR of compound 6cb (400 MHz, CDCl 3 ). Fig. S12. 13 C NMR of compound 6cb (100 MHz, CDCl 3 ). S8
Fig. S13. 1 H NMR of compound 6da (400 MHz, CDCl 3 ). Fig. S14. 13 C NMR of compound 6da (100 MHz, CDCl 3 ). S9
Fig. S15. 1 H NMR of compound 6db (400 MHz, CDCl 3 ). Fig. S16. 13 C NMR of compound 6db (100 MHz, CDCl 3 ). S10
Fig. S17. 1 H NMR of compound 6ea (400 MHz, CDCl 3 ). Fig. S18. 13 C NMR of compound 6ea (100 MHz, CDCl 3 ). S11
Fig. S19. 1 H NMR of compound 6eb (300 MHz, CDCl 3 ). Fig. S20. 13 C NMR of compound 6eb (150 MHz, CDCl 3 ). S12
Fig. S21. 1 H NMR of compound 6fa (400 MHz, CDCl 3 ). Fig. S22. 13 C NMR of compound 6fa (100 MHz, CDCl 3 ). S13
Fig. S23. 1 H NMR of compound 6fb (400 MHz, CDCl 3 ). Fig. S24. 13 C NMR of compound 6fb (100 MHz, CDCl 3 ). S14
Fig. S25. 1 H NMR of compound 6ga (400 MHz, CDCl 3 ). Fig. S26. 13 C NMR of compound 6ga (100 MHz, CDCl 3 ). S15
Fig. S27. 1 H NMR of compound 6gb (400 MHz, CDCl 3 ). Fig. S28. 13 C NMR of compound 6gb (100 MHz, CDCl 3 ). S16
Fig. S29. 1 H NMR of compound 6ha (400 MHz, CDCl 3 ). Fig. S30. 13 C NMR of compound 6ha (100 MHz, CDCl 3 ). S17
Fig. S31. 1 H NMR of compound 6hb (400 MHz, CDCl 3 ). Fig. S32. 13 C NMR of compound 6hb (100 MHz, CDCl 3 ). S18
Fig. S33. 1 H NMR of compound 6ia (400 MHz, CDCl 3 ). Fig. S34. 13 C NMR of compound 6ia (100 MHz, CDCl 3 ). S19
Fig. S35. 1 H NMR of compound 6ib (400 MHz, CDCl 3 ). Fig. S36. 13 C NMR of compound 6ib (100 MHz, CDCl 3 ). S20
Fig. S37. 1 H NMR of compound 6ja (400 MHz, CDCl 3 ). Fig. S38. 13 C NMR of compound 6ja (100 MHz, CDCl 3 ). S21
Fig. S39. 1 H NMR of compound 6jb (400 MHz, CDCl 3 ). Fig. S40. 13 C NMR of compound 6jb (100 MHz, CDCl 3 ). S22
Fig. S41. 1 H NMR of compound 6ka (400 MHz, CDCl 3 ). Fig. S42. 13 C NMR of compound 6ka (100 MHz, CDCl 3 ). S23
Fig. S43. 1 H NMR of compound 6kb (400 MHz, CDCl 3 ). Fig. S44. 13 C NMR of compound 6kb (100 MHz, CDCl 3 ). S24
Fig. S45. 1 H NMR of compound 6la (400 MHz, CDCl 3 ). Fig. S46. 13 C NMR of compound 6la (100 MHz, CDCl 3 ). S25
Fig. S47. 1 H NMR of compound 6lb (400 MHz, CDCl 3 ). Fig. S48. 13 C NMR of compound 6lb (100 MHz, CDCl 3 ). S26
Fig. S49. 1 H NMR of compound 6ma (400 MHz, CDCl 3 ). Fig. S50. 13 C NMR of compound 6ma (100 MHz, CDCl 3 ). S27
Fig. S51. 1 H NMR of compound 6mb (400 MHz, CDCl 3 ). Fig. S52. 13 C NMR of compound 6mb (100 MHz, CDCl 3 ). S28
Fig. S53. 1 H NMR of compound 6na (400 MHz, CDCl 3 ). Fig. S54. 13 C NMR of compound 6na (100 MHz, CDCl 3 ). S29
Fig. S55. 1 H NMR of compound 6nb (400 MHz, CDCl 3 ). Fig. S56. 13 C NMR of compound 6nb (150 MHz, CDCl 3 ). S30
Fig. S57. 1 H NMR of compound 6oa (400 MHz, CDCl 3 ). Fig. S58. 13 C NMR of compound 6oa (100 MHz, CDCl 3 ). S31
Fig. S59. 1 H NMR of compound 6ob (400 MHz, CDCl 3 ). Fig. S60. 13 C NMR of compound 6ob (100 MHz, CDCl 3 ). S32
Fig. S61. 1 H NMR of compound 6pa (400 MHz, CDCl 3 ). Fig. S62. 13 C NMR of compound 6pa (100 MHz, CDCl 3 ). S33
Fig. S63. 1 H NMR of compound 6pb (400 MHz, CDCl 3 ). Fig. S64. 13 C NMR of compound 6pb (100 MHz, CDCl 3 ). S34
Fig. S65. 1 H NMR of compound 6qa (400 MHz, CDCl 3 ). Fig. S66. 13 C NMR of compound 6qa (100 MHz, CDCl 3 ). S35
Fig. S67. 1 H NMR of compound 6qb (400 MHz, CDCl 3 ). Fig. S68. 13 C NMR of compound 6qb (100 MHz, CDCl 3 ). S36
Fig. S69. 1 H NMR of compound 6ra (400 MHz, CDCl 3 ). Fig. S70. 13 C NMR of compound 6ra (100 MHz, CDCl 3 ). S37
Fig. S71. 1 H NMR of compound 6rb (400 MHz, CDCl 3 ). Fig. S72. 13 C NMR of compound 6rb (100 MHz, CDCl 3 ). S38
Fig. S73. 1 H NMR of compound 6sa (400 MHz, CDCl 3 ). Fig. S74. 13 C NMR of compound 6sa (100 MHz, CDCl 3 ). S39
Fig. S75. 1 H NMR of compound 6sb (400 MHz, CDCl 3 ). Fig. S76. 13 C NMR of compound 6sb (100 MHz, CDCl 3 ). S40
Fig. S77. 1 H NMR of compound 6ta (400 MHz, CDCl 3 ). Fig. S78. 13 C NMR of compound 6ta (100 MHz, CDCl 3 ). S41
Fig. S79. 1 H NMR of compound 6tb (400 MHz, CDCl 3 ). Fig. S80. 13 C NMR of compound 6tb (100 MHz, CDCl 3 ). S42
Fig. S81. 1 H NMR of compound 6ua (400 MHz, CDCl 3 ). Fig. S82. 13 C NMR of compound 6ua (100 MHz, CDCl 3 ). S43
Fig. S83. 1 H NMR of compound 6ub (400 MHz, CDCl 3 ). Fig. S84. 13 C NMR of compound 6ub (100 MHz, CDCl 3 ). S44
Fig. S85. 1 H NMR of compound 6va (400 MHz, CDCl 3 ). Fig. S86. 13 C NMR of compound 6va (100 MHz, CDCl 3 ). S45
Fig. S87. 1 H NMR of compound 6vb (400 MHz, CDCl 3 ). Fig. S88. 13 C NMR of compound 6vb (100 MHz, CDCl 3 ). S46
Fig. S89. 1 H NMR of compound 6wa (400 MHz, CDCl 3 ). Fig. S90. 13 C NMR of compound 6wa (100 MHz, CDCl 3 ). S47
Fig. S91. 1 H NMR of compound 6wb (400 MHz, CDCl 3 ). Fig. S92. 13 C NMR of compound 6wb (100 MHz, CDCl 3 ). S48
Fig. S93. 1 H NMR of compound 6xa (400 MHz, CDCl 3 ). Fig. S94. 13 C NMR of compound 6xa (100 MHz, CDCl 3 ). S49
Fig. S95. 1 H NMR of compound 6xb (400 MHz, CDCl 3 ). Fig. S96. 13 C NMR of compound 6xb (100 MHz, CDCl 3 ). S50
Fig. S97. 1 H NMR of compound 6y (400 MHz, CDCl 3 ) Fig. S98. 13 C NMR of compound 6y (100 MHz, CDCl 3 ). S51
Fig. S99. 1 H NMR of compound 7aa (400 MHz, CDCl 3 ). Fig. S100. 13 C NMR of compound 7aa (100 MHz, CDCl 3 ). S52
Fig. S101. 1 H NMR of compound 7ab (400 MHz, CDCl 3 ). Fig. S102. 13 C NMR of compound 7ab (150 MHz, CDCl 3 ). S53
Fig. S103. 1 H NMR of compound 7bb (400 MHz, CDCl 3 ). Fig. S104. 13 C NMR of compound 7bb (100 MHz, CDCl 3 ). S54
Fig. S105. 1 H NMR of compound 7b (400 MHz, CDCl 3 ). Fig. S106. 13 C NMR of compound 7b (100 MHz, CDCl 3 ). S55
Fig. S107. 1 H NMR of compound 8 (400 MHz, CDCl 3 ). Fig. S108. Selected key 3 J coupling values of compound 8 s 1 H NMR (400 MHz, CDCl 3 ). S56
Fig. S109. 13 C NMR of compound 8 (100 MHz, CDCl 3 ). Naphthyl residue CO2Me NMe CO2Et H5a H4 H3 H5e H2 H1 CO2Et C1-Me Fig. S110. NOESY spectrum of compound 8 (400 MHz, CDCl 3 ). S57
CO2Me NMe Naphthyl residue CO2Et H4 H3 H5e H2 H5a H1 CO2Et C1-Me Fig. S111. 1 H- 1 H COSY spectrum of compound 8 (400 MHz, CDCl 3 ). S58
3. X-ray of compound 6hb, 6na, 7aa and 7bb 6hb Thermal ellipsoids are drawn at the 35% probability level 6na Thermal ellipsoids are drawn at the 35% probability level S59
7aa Thermal ellipsoids are drawn at the 35% probability level 7bb Thermal ellipsoids are drawn at the 35% probability level The X-ray structural data were deposited at the Cambridge Crystallographic Data Center. CCDC 1574988, 1574989, 1574990 and 1574993, contains the supplementary crystallographic data. S60