Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Ying-Chun Chen' _publ_contact_author_address ; Department of Medicinal Chemistry West China School of Pharmacy Chengdu 610041 CHINA ; _publ_contact_author_email YCCHENHUAXI@YAHOO.COM.CN _publ_section_title ; Organocatalytic Enantioselective Indole Alkylations of a,b-Unsaturated Ketones ; loop_ _publ_author_name 'Ying-Chun Chen.' 'Wei Chen.' 'Li-Sheng Ding.' 'Wei Du.' 'Rui Li.' 'Yong Wu.' ; Lei Yue ; data_4bh _database_code_depnum_ccdc_archive 'CCDC 624251' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H20 Cl N O2' _chemical_formula_weight 341.82 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' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 5.1480(1) _cell_length_b 15.8080(3) _cell_length_c 21.3073(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1733.98(6) _cell_formula_units_Z 4 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 16793 _cell_measurement_theta_min 3.15 _cell_measurement_theta_max 27.52 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.309 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 0.232 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8831 _exptl_absorpt_correction_T_max 0.9638 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Rotating Anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 17187 _diffrn_reflns_av_R_equivalents 0.0185 _diffrn_reflns_av_sigmaI/netI 0.0146 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 3.14 _diffrn_reflns_theta_max 27.48 _reflns_number_total 3985 _reflns_number_gt 3914 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Rapid Auto Version 3.0 (Rigaku 2004)' _computing_cell_refinement 'Rapid Auto Version 3.0 (Rigaku 2004)' _computing_data_reduction 'Rapid Auto Version 3.0 (Rigaku 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _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^)+(0.0429P)^2^+0.4980P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0117(15) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.02(5) _refine_ls_number_reflns 3985 _refine_ls_number_parameters 224 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0302 _refine_ls_R_factor_gt 0.0296 _refine_ls_wR_factor_ref 0.0782 _refine_ls_wR_factor_gt 0.0778 _refine_ls_goodness_of_fit_ref 1.008 _refine_ls_restrained_S_all 1.008 _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 Cl Cl 0.83456(11) 0.19448(2) 0.34804(2) 0.05003(14) Uani 1 1 d . . . O1 O 0.3698(2) 0.62837(7) 0.29070(5) 0.0334(2) Uani 1 1 d . . . O2 O 0.5009(2) 0.56043(6) 0.63379(5) 0.0306(2) Uani 1 1 d . . . N N 1.0710(2) 0.69158(7) 0.47872(6) 0.0277(2) Uani 1 1 d . . . C1 C 0.9087(3) 0.68491(8) 0.42780(6) 0.0232(3) Uani 1 1 d . . . C2 C 0.8857(3) 0.73581(8) 0.37437(7) 0.0296(3) Uani 1 1 d . . . H2 H 0.9934 0.7840 0.3686 0.035 Uiso 1 1 calc R . . C3 C 0.7020(3) 0.71380(8) 0.33057(6) 0.0304(3) Uani 1 1 d . . . H3 H 0.6834 0.7471 0.2937 0.036 Uiso 1 1 calc R . . C4 C 0.5400(3) 0.64257(8) 0.33917(6) 0.0246(3) Uani 1 1 d . . . C5 C 0.5608(2) 0.59237(8) 0.39193(6) 0.0206(2) Uani 1 1 d . . . H5 H 0.4505 0.5448 0.3977 0.025 Uiso 1 1 calc R . . C6 C 0.7498(2) 0.61353(7) 0.43692(6) 0.0188(2) Uani 1 1 d . . . C7 C 0.8294(2) 0.57493(7) 0.49493(5) 0.0200(2) Uani 1 1 d . . . C8 C 1.0279(3) 0.62371(8) 0.51799(6) 0.0250(3) Uani 1 1 d . . . H8 H 1.1218 0.6124 0.5555 0.030 Uiso 1 1 calc R . . C9 C 0.1880(3) 0.56195(10) 0.29842(6) 0.0308(3) Uani 1 1 d . . . H9A H 0.0859 0.5718 0.3365 0.037 Uiso 1 1 calc R . . H9B H 0.2806 0.5080 0.3021 0.037 Uiso 1 1 calc R . . H9C H 0.0719 0.5601 0.2620 0.037 Uiso 1 1 calc R . . C10 C 0.7186(2) 0.49468(7) 0.52147(5) 0.0193(2) Uani 1 1 d . . . H10 H 0.5274 0.5036 0.5264 0.023 Uiso 1 1 calc R . . C11 C 0.7550(2) 0.41934(7) 0.47781(5) 0.0197(2) Uani 1 1 d . . . C12 C 0.9594(3) 0.41431(8) 0.43527(6) 0.0250(3) Uani 1 1 d . . . H12 H 1.0824 0.4590 0.4332 0.030 Uiso 1 1 calc R . . C13 C 0.9867(3) 0.34486(9) 0.39572(6) 0.0291(3) Uani 1 1 d . . . H13 H 1.1268 0.3421 0.3668 0.035 Uiso 1 1 calc R . . C14 C 0.8077(3) 0.28017(8) 0.39910(6) 0.0298(3) Uani 1 1 d . . . C15 C 0.6043(3) 0.28262(9) 0.44108(7) 0.0322(3) Uani 1 1 d . . . H15 H 0.4831 0.2374 0.4432 0.039 Uiso 1 1 calc R . . C16 C 0.5795(3) 0.35232(8) 0.48022(7) 0.0273(3) Uani 1 1 d . . . H16 H 0.4397 0.3544 0.5093 0.033 Uiso 1 1 calc R . . C17 C 0.8279(3) 0.47443(8) 0.58699(6) 0.0233(2) Uani 1 1 d . . . H17A H 0.7876 0.4148 0.5975 0.028 Uiso 1 1 calc R . . H17B H 1.0192 0.4806 0.5861 0.028 Uiso 1 1 calc R . . C18 C 0.7179(2) 0.53150(8) 0.63781(5) 0.0220(2) Uani 1 1 d . . . C19 C 0.8859(3) 0.54562(11) 0.69415(6) 0.0346(3) Uani 1 1 d . . . H19A H 1.0547 0.5688 0.6800 0.041 Uiso 1 1 calc R . . H19B H 0.9205 0.4902 0.7142 0.041 Uiso 1 1 calc R . . C20 C 0.7726(3) 0.60491(11) 0.74314(7) 0.0388(4) Uani 1 1 d . . . H20A H 0.5979 0.5858 0.7546 0.047 Uiso 1 1 calc R . . H20B H 0.7632 0.6623 0.7259 0.047 Uiso 1 1 calc R . . H20C H 0.8837 0.6049 0.7805 0.047 Uiso 1 1 calc R . . H0N H 1.206(4) 0.7268(13) 0.4834(9) 0.048(5) Uiso 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 Cl 0.0799(3) 0.03103(18) 0.0391(2) -0.01599(15) -0.0055(2) 0.0019(2) O1 0.0301(5) 0.0457(6) 0.0244(4) 0.0119(4) -0.0025(4) 0.0012(5) O2 0.0257(5) 0.0329(5) 0.0332(5) -0.0025(4) 0.0001(4) 0.0077(4) N 0.0272(5) 0.0228(5) 0.0330(6) -0.0070(5) 0.0027(5) -0.0079(5) C1 0.0248(6) 0.0163(5) 0.0284(6) -0.0040(5) 0.0072(5) -0.0017(5) C2 0.0355(7) 0.0162(5) 0.0370(7) 0.0027(5) 0.0115(6) -0.0022(5) C3 0.0371(7) 0.0233(6) 0.0307(6) 0.0104(5) 0.0097(6) 0.0049(6) C4 0.0230(6) 0.0272(6) 0.0235(6) 0.0043(5) 0.0038(5) 0.0047(5) C5 0.0195(5) 0.0200(5) 0.0223(5) 0.0033(4) 0.0018(4) 0.0002(4) C6 0.0191(5) 0.0151(5) 0.0221(5) -0.0003(4) 0.0045(4) 0.0018(4) C7 0.0210(5) 0.0182(5) 0.0209(5) -0.0022(4) 0.0000(4) 0.0011(5) C8 0.0246(6) 0.0240(6) 0.0263(6) -0.0060(5) -0.0009(5) -0.0012(5) C9 0.0255(6) 0.0423(8) 0.0245(6) 0.0002(5) -0.0018(5) 0.0030(6) C10 0.0195(5) 0.0188(5) 0.0197(5) 0.0014(4) -0.0010(4) 0.0020(4) C11 0.0215(5) 0.0184(5) 0.0193(5) 0.0021(4) -0.0040(4) 0.0012(4) C12 0.0267(6) 0.0216(6) 0.0269(6) -0.0001(5) 0.0004(5) -0.0005(5) C13 0.0360(7) 0.0288(6) 0.0223(6) -0.0007(5) 0.0022(5) 0.0060(6) C14 0.0446(8) 0.0204(6) 0.0245(6) -0.0038(5) -0.0098(6) 0.0055(6) C15 0.0370(8) 0.0221(6) 0.0376(7) -0.0003(5) -0.0078(6) -0.0047(6) C16 0.0270(6) 0.0233(6) 0.0316(7) 0.0018(5) -0.0018(5) -0.0027(5) C17 0.0271(6) 0.0221(5) 0.0207(5) 0.0008(4) -0.0020(5) 0.0070(5) C18 0.0250(6) 0.0202(5) 0.0209(6) 0.0041(4) 0.0020(5) 0.0017(5) C19 0.0344(7) 0.0471(8) 0.0222(6) -0.0052(6) -0.0035(6) 0.0101(7) C20 0.0443(9) 0.0466(9) 0.0255(7) -0.0083(6) 0.0031(6) 0.0008(7) _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 Cl C14 1.7428(13) . ? O1 C4 1.3726(17) . ? O1 C9 1.4159(18) . ? O2 C18 1.2102(17) . ? N C1 1.3734(18) . ? N C8 1.3786(18) . ? N H0N 0.89(2) . ? C1 C2 1.3991(18) . ? C1 C6 1.4074(17) . ? C2 C3 1.373(2) . ? C2 H2 0.9500 . ? C3 C4 1.4131(19) . ? C3 H3 0.9500 . ? C4 C5 1.3802(17) . ? C5 C6 1.4062(17) . ? C5 H5 0.9500 . ? C6 C7 1.4381(16) . ? C7 C8 1.3712(17) . ? C7 C10 1.5015(16) . ? C8 H8 0.9500 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 C11 1.5228(16) . ? C10 C17 1.5387(16) . ? C10 H10 1.0000 . ? C11 C12 1.3911(18) . ? C11 C16 1.3936(17) . ? C12 C13 1.3911(18) . ? C12 H12 0.9500 . ? C13 C14 1.378(2) . ? C13 H13 0.9500 . ? C14 C15 1.378(2) . ? C15 C16 1.388(2) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 C18 1.5190(17) . ? C17 H17A 0.9900 . ? C17 H17B 0.9900 . ? C18 C19 1.4964(18) . ? C19 C20 1.519(2) . ? C19 H19A 0.9900 . ? C19 H19B 0.9900 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? 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 C4 O1 C9 117.11(10) . . ? C1 N C8 108.77(11) . . ? C1 N H0N 127.4(13) . . ? C8 N H0N 122.8(13) . . ? N C1 C2 130.57(12) . . ? N C1 C6 107.83(11) . . ? C2 C1 C6 121.60(12) . . ? C3 C2 C1 117.76(12) . . ? C3 C2 H2 121.1 . . ? C1 C2 H2 121.1 . . ? C2 C3 C4 121.34(12) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? O1 C4 C5 124.63(12) . . ? O1 C4 C3 114.17(11) . . ? C5 C4 C3 121.19(12) . . ? C4 C5 C6 118.18(11) . . ? C4 C5 H5 120.9 . . ? C6 C5 H5 120.9 . . ? C5 C6 C1 119.93(11) . . ? C5 C6 C7 133.02(11) . . ? C1 C6 C7 107.04(11) . . ? C8 C7 C6 106.37(11) . . ? C8 C7 C10 128.56(11) . . ? C6 C7 C10 125.02(11) . . ? C7 C8 N 109.88(11) . . ? C7 C8 H8 125.1 . . ? N C8 H8 125.1 . . ? O1 C9 H9A 109.5 . . ? O1 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? O1 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C7 C10 C11 112.58(10) . . ? C7 C10 C17 112.24(10) . . ? C11 C10 C17 110.27(9) . . ? C7 C10 H10 107.1 . . ? C11 C10 H10 107.1 . . ? C17 C10 H10 107.1 . . ? C12 C11 C16 118.10(12) . . ? C12 C11 C10 122.40(11) . . ? C16 C11 C10 119.49(11) . . ? C13 C12 C11 121.08(12) . . ? C13 C12 H12 119.5 . . ? C11 C12 H12 119.5 . . ? C14 C13 C12 119.10(13) . . ? C14 C13 H13 120.5 . . ? C12 C13 H13 120.5 . . ? C15 C14 C13 121.41(12) . . ? C15 C14 Cl 119.16(11) . . ? C13 C14 Cl 119.41(12) . . ? C14 C15 C16 118.84(13) . . ? C14 C15 H15 120.6 . . ? C16 C15 H15 120.6 . . ? C15 C16 C11 121.46(13) . . ? C15 C16 H16 119.3 . . ? C11 C16 H16 119.3 . . ? C18 C17 C10 112.77(10) . . ? C18 C17 H17A 109.0 . . ? C10 C17 H17A 109.0 . . ? C18 C17 H17B 109.0 . . ? C10 C17 H17B 109.0 . . ? H17A C17 H17B 107.8 . . ? O2 C18 C19 122.29(12) . . ? O2 C18 C17 121.20(12) . . ? C19 C18 C17 116.42(11) . . ? C18 C19 C20 114.91(13) . . ? C18 C19 H19A 108.5 . . ? C20 C19 H19A 108.5 . . ? C18 C19 H19B 108.5 . . ? C20 C19 H19B 108.5 . . ? H19A C19 H19B 107.5 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C8 N C1 C2 -177.33(13) . . . . ? C8 N C1 C6 3.19(14) . . . . ? N C1 C2 C3 -179.55(13) . . . . ? C6 C1 C2 C3 -0.14(19) . . . . ? C1 C2 C3 C4 0.5(2) . . . . ? C9 O1 C4 C5 5.96(19) . . . . ? C9 O1 C4 C3 -175.23(11) . . . . ? C2 C3 C4 O1 -178.97(12) . . . . ? C2 C3 C4 C5 -0.1(2) . . . . ? O1 C4 C5 C6 178.19(12) . . . . ? C3 C4 C5 C6 -0.54(19) . . . . ? C4 C5 C6 C1 0.85(17) . . . . ? C4 C5 C6 C7 -177.70(12) . . . . ? N C1 C6 C5 179.02(11) . . . . ? C2 C1 C6 C5 -0.52(18) . . . . ? N C1 C6 C7 -2.10(13) . . . . ? C2 C1 C6 C7 178.37(11) . . . . ? C5 C6 C7 C8 178.91(13) . . . . ? C1 C6 C7 C8 0.23(13) . . . . ? C5 C6 C7 C10 1.4(2) . . . . ? C1 C6 C7 C10 -177.30(11) . . . . ? C6 C7 C8 N 1.74(14) . . . . ? C10 C7 C8 N 179.15(12) . . . . ? C1 N C8 C7 -3.12(15) . . . . ? C8 C7 C10 C11 -116.99(14) . . . . ? C6 C7 C10 C11 59.98(15) . . . . ? C8 C7 C10 C17 8.15(17) . . . . ? C6 C7 C10 C17 -174.89(11) . . . . ? C7 C10 C11 C12 27.70(16) . . . . ? C17 C10 C11 C12 -98.51(14) . . . . ? C7 C10 C11 C16 -152.60(11) . . . . ? C17 C10 C11 C16 81.20(14) . . . . ? C16 C11 C12 C13 0.67(19) . . . . ? C10 C11 C12 C13 -179.62(11) . . . . ? C11 C12 C13 C14 -0.1(2) . . . . ? C12 C13 C14 C15 -0.5(2) . . . . ? C12 C13 C14 Cl 178.00(10) . . . . ? C13 C14 C15 C16 0.6(2) . . . . ? Cl C14 C15 C16 -177.97(11) . . . . ? C14 C15 C16 C11 0.0(2) . . . . ? C12 C11 C16 C15 -0.64(19) . . . . ? C10 C11 C16 C15 179.64(12) . . . . ? C7 C10 C17 C18 73.80(14) . . . . ? C11 C10 C17 C18 -159.81(11) . . . . ? C10 C17 C18 O2 30.32(17) . . . . ? C10 C17 C18 C19 -153.02(12) . . . . ? O2 C18 C19 C20 -5.0(2) . . . . ? C17 C18 C19 C20 178.41(13) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N H0N N 0.89(2) 2.42(2) 3.2954(14) 166.2(18) 4_566 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.375 _refine_diff_density_min -0.442 _refine_diff_density_rms 0.038