# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Huanfeng Jiang' _publ_contact_author_email JIANGHF@SCUT.EDU.CN _publ_section_title ; L-Proline-Catalyzed Synthesis of Highly Functionalized Multisubstituted 1,4-Dihydropyridines ; loop_ _publ_author_name 'Huanfeng Jiang' 'Hua Cao' 'Xiaohang Liu' 'Ronghuan Mai' 'Qiuhua Zhu' # Attachment '5ckaa.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 744016' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H20 Cl N O2' _chemical_formula_sum 'C22 H20 Cl N O2' _chemical_formula_weight 365.84 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbca _symmetry_space_group_name_Hall '-P 2ac 2ab ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 17.530(3) _cell_length_b 14.759(3) _cell_length_c 14.559(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3766.8(13) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 4520 _cell_measurement_theta_min 1.36 _cell_measurement_theta_max 28 _exptl_crystal_description block _exptl_crystal_colour brown _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.290 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1536 _exptl_absorpt_coefficient_mu 0.218 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.951 _exptl_absorpt_correction_T_max 0.964 _exptl_absorpt_process_details '(Jacobson, 1998)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku/MSC Mercury CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 26778 _diffrn_reflns_av_R_equivalents 0.0524 _diffrn_reflns_av_sigmaI/netI 0.0338 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.03 _diffrn_reflns_theta_max 25.20 _reflns_number_total 3357 _reflns_number_gt 1942 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'RAPID-AUTO (Rigaku, 1998)' _computing_cell_refinement RAPID-AUTO _computing_data_reduction 'CrystalStructure (Rigaku/MSC, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEPII (Johnson, 1976)' _computing_publication_material SHELXL97 _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1303P)^2^+0.2046P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3357 _refine_ls_number_parameters 232 _refine_ls_number_restraints 7 _refine_ls_R_factor_all 0.1059 _refine_ls_R_factor_gt 0.0663 _refine_ls_wR_factor_ref 0.2385 _refine_ls_wR_factor_gt 0.2090 _refine_ls_goodness_of_fit_ref 1.147 _refine_ls_restrained_S_all 1.146 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl 0.49948(7) 0.71496(7) 1.05398(9) 0.0989(5) Uani 1 1 d . . . O1 O 0.56610(13) 0.64277(14) 0.8152(2) 0.0819(9) Uani 1 1 d . . . C22 C 0.7122(2) 0.9185(3) 0.8484(4) 0.1011(11) Uani 1 1 d U . . H22A H 0.7535 0.9608 0.8535 0.152 Uiso 1 1 calc R . . H22B H 0.7071 0.8995 0.7857 0.152 Uiso 1 1 calc R . . H22C H 0.7223 0.8667 0.8864 0.152 Uiso 1 1 calc R . . N1 N 0.43360(13) 0.91737(15) 0.8398(2) 0.0590(7) Uani 1 1 d . . . C1 C 0.45704(16) 0.62308(17) 0.9027(2) 0.0558(8) Uani 1 1 d . . . C2 C 0.45144(18) 0.62979(19) 0.9967(3) 0.0635(9) Uani 1 1 d . . . C3 C 0.4103(2) 0.5682(2) 1.0469(3) 0.0825(12) Uani 1 1 d . . . H3 H 0.4083 0.5732 1.1105 0.099 Uiso 1 1 calc R . . C4 C 0.3723(2) 0.4996(2) 1.0042(4) 0.0891(14) Uani 1 1 d . . . H4 H 0.3441 0.4583 1.0384 0.107 Uiso 1 1 calc R . . C5 C 0.3758(2) 0.4917(2) 0.9115(4) 0.0836(12) Uani 1 1 d . . . H5 H 0.3490 0.4457 0.8821 0.100 Uiso 1 1 calc R . . C6 C 0.41864(17) 0.5514(2) 0.8610(3) 0.0717(10) Uani 1 1 d . . . H6 H 0.4221 0.5438 0.7978 0.086 Uiso 1 1 calc R . . C7 C 0.50942(16) 0.6807(2) 0.8472(3) 0.0587(8) Uani 1 1 d . . . C8 C 0.49926(15) 0.77740(19) 0.8343(3) 0.0560(8) Uani 1 1 d . . . C9 C 0.43261(15) 0.82349(19) 0.8419(2) 0.0564(8) Uani 1 1 d . . . C10 C 0.50094(15) 0.9640(2) 0.8618(3) 0.0573(8) Uani 1 1 d . . . C11 C 0.56870(16) 0.92118(19) 0.8517(3) 0.0586(8) Uani 1 1 d . . . C12 C 0.56874(18) 0.8301(2) 0.8058(3) 0.0699(10) Uani 1 1 d . . . H12A H 0.6144 0.7969 0.8229 0.084 Uiso 1 1 calc R . . H12B H 0.5689 0.8378 0.7396 0.084 Uiso 1 1 calc R . . C13 C 0.35614(16) 0.78090(18) 0.8505(3) 0.0635(10) Uani 1 1 d . . . C14 C 0.3118(2) 0.7956(2) 0.9265(4) 0.0831(13) Uani 1 1 d . . . H14 H 0.3309 0.8291 0.9756 0.100 Uiso 1 1 calc R . . C15 C 0.2386(2) 0.7607(3) 0.9303(5) 0.116(2) Uani 1 1 d . . . H15 H 0.2083 0.7711 0.9816 0.139 Uiso 1 1 calc R . . C16 C 0.2110(3) 0.7111(3) 0.8587(6) 0.125(3) Uani 1 1 d . . . H16 H 0.1615 0.6884 0.8613 0.150 Uiso 1 1 calc R . . C17 C 0.2537(3) 0.6946(3) 0.7853(5) 0.116(2) Uani 1 1 d . . . H17 H 0.2344 0.6594 0.7377 0.140 Uiso 1 1 calc R . . C18 C 0.3272(2) 0.7296(2) 0.7792(4) 0.0881(13) Uani 1 1 d . . . H18 H 0.3567 0.7186 0.7273 0.106 Uiso 1 1 calc R . . C19 C 0.36359(18) 0.9686(2) 0.8221(3) 0.0756(11) Uani 1 1 d . . . H19A H 0.3436 0.9911 0.8790 0.113 Uiso 1 1 calc R . . H19B H 0.3266 0.9297 0.7936 0.113 Uiso 1 1 calc R . . H19C H 0.3747 1.0185 0.7820 0.113 Uiso 1 1 calc R . . C20 C 0.49033(18) 1.0580(2) 0.8964(3) 0.0690(10) Uani 1 1 d . . . H20A H 0.5364 1.0782 0.9256 0.104 Uiso 1 1 calc R . . H20B H 0.4493 1.0591 0.9400 0.104 Uiso 1 1 calc R . . H20C H 0.4784 1.0974 0.8459 0.104 Uiso 1 1 calc R . . C21 C 0.6412(2) 0.9619(3) 0.8785(4) 0.1011(11) Uani 1 1 d U . . O2 O 0.64906(17) 1.0309(3) 0.9192(4) 0.173(2) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.1438(11) 0.0798(7) 0.0731(9) -0.0142(5) -0.0215(6) -0.0093(5) O1 0.0794(16) 0.0637(13) 0.102(2) -0.0056(13) 0.0303(14) 0.0063(11) C22 0.0662(16) 0.113(2) 0.124(3) -0.033(2) -0.0015(16) -0.0098(14) N1 0.0548(14) 0.0478(12) 0.074(2) 0.0014(12) -0.0024(12) -0.0012(10) C1 0.0563(16) 0.0510(15) 0.060(3) -0.0034(14) 0.0031(14) 0.0062(12) C2 0.0700(19) 0.0551(17) 0.065(3) -0.0038(15) -0.0001(17) 0.0086(13) C3 0.101(3) 0.075(2) 0.071(3) 0.012(2) 0.018(2) 0.016(2) C4 0.088(3) 0.064(2) 0.115(5) 0.013(2) 0.027(2) -0.0013(17) C5 0.082(2) 0.062(2) 0.106(4) -0.003(2) 0.007(2) -0.0080(16) C6 0.074(2) 0.0627(19) 0.078(3) -0.0109(17) 0.0056(18) -0.0078(15) C7 0.0589(17) 0.0556(17) 0.061(2) -0.0087(15) 0.0022(15) 0.0014(12) C8 0.0546(18) 0.0525(17) 0.061(2) -0.0049(14) 0.0032(14) -0.0049(11) C9 0.0555(17) 0.0534(15) 0.060(2) -0.0020(13) -0.0036(14) -0.0058(12) C10 0.0643(19) 0.0531(16) 0.055(2) -0.0002(14) 0.0004(14) -0.0070(12) C11 0.0549(17) 0.0571(16) 0.064(2) -0.0025(14) 0.0051(15) -0.0093(12) C12 0.0663(19) 0.0615(17) 0.082(3) -0.0083(17) 0.0165(17) -0.0085(14) C13 0.0495(16) 0.0486(16) 0.092(3) 0.0052(16) -0.0084(17) -0.0001(11) C14 0.0569(19) 0.067(2) 0.126(4) 0.011(2) 0.008(2) -0.0034(15) C15 0.062(2) 0.077(2) 0.209(7) 0.020(3) 0.023(3) -0.001(2) C16 0.060(3) 0.073(3) 0.242(9) 0.022(4) -0.016(4) -0.011(2) C17 0.087(3) 0.068(2) 0.195(7) 0.002(3) -0.063(4) -0.010(2) C18 0.081(2) 0.067(2) 0.117(4) -0.001(2) -0.036(2) -0.0064(16) C19 0.067(2) 0.0608(18) 0.099(4) 0.0145(18) -0.0132(18) 0.0022(14) C20 0.081(2) 0.0518(17) 0.075(3) -0.0065(16) 0.0003(17) -0.0039(13) C21 0.0662(16) 0.113(2) 0.124(3) -0.033(2) -0.0015(16) -0.0098(14) O2 0.084(2) 0.140(3) 0.294(6) -0.117(4) -0.011(3) -0.0237(18) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cl1 C2 1.728(3) . ? O1 C7 1.232(3) . ? C22 C21 1.465(5) . ? C22 H22A 0.9600 . ? C22 H22B 0.9600 . ? C22 H22C 0.9600 . ? N1 C9 1.386(4) . ? N1 C10 1.404(3) . ? N1 C19 1.464(4) . ? C1 C2 1.376(5) . ? C1 C6 1.393(4) . ? C1 C7 1.490(4) . ? C2 C3 1.372(5) . ? C3 C4 1.362(6) . ? C3 H3 0.9300 . ? C4 C5 1.355(6) . ? C4 H4 0.9300 . ? C5 C6 1.371(5) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 C8 1.450(4) . ? C8 C9 1.357(4) . ? C8 C12 1.503(4) . ? C9 C13 1.486(4) . ? C10 C11 1.353(4) . ? C10 C20 1.488(4) . ? C11 C21 1.459(5) . ? C11 C12 1.502(4) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 C14 1.369(6) . ? C13 C18 1.381(5) . ? C14 C15 1.385(5) . ? C14 H14 0.9300 . ? C15 C16 1.363(8) . ? C15 H15 0.9300 . ? C16 C17 1.327(9) . ? C16 H16 0.9300 . ? C17 C18 1.390(6) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C20 H20C 0.9600 . ? C21 O2 1.187(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C9 N1 C10 119.7(2) . . ? C9 N1 C19 120.6(2) . . ? C10 N1 C19 119.5(2) . . ? C2 C1 C6 116.9(3) . . ? C2 C1 C7 122.8(3) . . ? C6 C1 C7 119.7(3) . . ? C3 C2 C1 121.3(3) . . ? C3 C2 Cl1 118.8(3) . . ? C1 C2 Cl1 119.9(2) . . ? C4 C3 C2 120.4(4) . . ? C4 C3 H3 119.8 . . ? C2 C3 H3 119.8 . . ? C5 C4 C3 119.8(4) . . ? C5 C4 H4 120.1 . . ? C3 C4 H4 120.1 . . ? C4 C5 C6 120.2(4) . . ? C4 C5 H5 119.9 . . ? C6 C5 H5 119.9 . . ? C5 C6 C1 121.3(4) . . ? C5 C6 H6 119.3 . . ? C1 C6 H6 119.3 . . ? O1 C7 C8 119.8(3) . . ? O1 C7 C1 116.2(3) . . ? C8 C7 C1 123.8(3) . . ? C9 C8 C7 126.1(3) . . ? C9 C8 C12 117.5(3) . . ? C7 C8 C12 116.4(2) . . ? C8 C9 N1 119.3(2) . . ? C8 C9 C13 124.9(3) . . ? N1 C9 C13 115.9(2) . . ? C11 C10 N1 119.0(3) . . ? C11 C10 C20 125.6(3) . . ? N1 C10 C20 115.4(2) . . ? C10 C11 C21 122.9(3) . . ? C10 C11 C12 117.8(3) . . ? C21 C11 C12 119.1(3) . . ? C11 C12 C8 109.9(3) . . ? C11 C12 H12A 109.7 . . ? C8 C12 H12A 109.7 . . ? C11 C12 H12B 109.7 . . ? C8 C12 H12B 109.7 . . ? H12A C12 H12B 108.2 . . ? C14 C13 C18 119.1(3) . . ? C14 C13 C9 120.8(3) . . ? C18 C13 C9 120.0(4) . . ? C13 C14 C15 119.9(5) . . ? C13 C14 H14 120.0 . . ? C15 C14 H14 120.0 . . ? C16 C15 C14 120.0(5) . . ? C16 C15 H15 120.0 . . ? C14 C15 H15 120.0 . . ? C17 C16 C15 120.9(5) . . ? C17 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? C16 C17 C18 120.4(5) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C13 C18 C17 119.7(5) . . ? C13 C18 H18 120.1 . . ? C17 C18 H18 120.1 . . ? N1 C19 H19A 109.5 . . ? N1 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? N1 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? C10 C20 H20A 109.5 . . ? C10 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C10 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? O2 C21 C11 126.0(4) . . ? O2 C21 C22 115.2(3) . . ? C11 C21 C22 118.7(4) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 25.20 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.768 _refine_diff_density_min -0.634 _refine_diff_density_rms 0.049