# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2006 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Armando Cordova' _publ_contact_author_address ; Department of Organic Chemistry Stockholm University Arrhenius Lab Stockholm SE-10691 SWEDEN ; _publ_contact_author_email ACORDOVA@ORGAN.SU.SE _publ_section_title ; Organocatalytic enantioselective conjugate addition of aldehydes to maleimides ; loop_ _publ_author_name 'Armando Cordova' 'Lars Eriksson' 'Mahmoud Sayah' 'Henrik Sunden' 'Yongmei Xu' 'Gui-Ling Zhao' data_a10_100k _database_code_depnum_ccdc_archive 'CCDC 623384' # Compound name _chemical_name_systematic ? # Compound synonym (drug name, brand name, etc.) _chemical_name_common ? # Formula _chemical_formula_sum 'C15 H16 Br N O4' _chemical_formula_moiety 'C15 H16 Br N O4' # Formula weight _chemical_formula_weight 354.20 # source of scattering factors 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' Br Br -0.2901 2.4595 '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' # Colour _exptl_crystal_colour colourless # Melting point (in K) _chemical_melting_point ? # Crystal habit (for example: prism) _exptl_crystal_description prism # Crystallization solvent _exptl_crystal_preparation 'methylenedichloride : pentane' # Unit cell parameters with standard deviations # (unit cell lengths in Angstroms) _cell_length_a 5.4015(2) _cell_length_b 10.6598(4) _cell_length_c 13.0093(5) _cell_angle_alpha 90.00 _cell_angle_beta 99.248(4) _cell_angle_gamma 90.00 # Unit cell volume (in cubic Angstroms) _cell_volume 739.33(5) # Space group symbol (in Hermann-Mauguin notation) and # symmetry equivalent positions _symmetry_space_group_name_H-M 'P 21' _symmetry_space_group_name_Hall 'P 2yb' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' # Z value _cell_formula_units_Z 2 # Calculated density _exptl_crystal_density_diffrn 1.591 # Temperature of study (in K) _diffrn_ambient_temperature 100(1) # R-factor _refine_ls_R_factor_all 0.0985 _refine_ls_R_factor_gt 0.0363 _refine_ls_wR_factor_ref 0.0460 _refine_ls_wR_factor_gt 0.0396 # Atomic coordinates with standard deviations 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 Br1 Br 0.13272(8) 0.30485(6) -0.07940(3) 0.02698(11) Uani 1 1 d . . . C2 C 0.1807(8) 0.2062(4) 0.0442(3) 0.0188(10) Uani 1 1 d . . . C3 C 0.0144(7) 0.2248(3) 0.1141(3) 0.0174(10) Uani 1 1 d . . . H3 H -0.1214 0.2819 0.0984 0.021 Uiso 1 1 calc R . . C4 C 0.0503(7) 0.1586(3) 0.2068(3) 0.0143(9) Uani 1 1 d . . . H4 H -0.0629 0.1689 0.2551 0.017 Uiso 1 1 calc R . . C5 C 0.2491(9) 0.0786(4) 0.2286(4) 0.0106(12) Uani 1 1 d . . . C6 C 0.4124(8) 0.0578(4) 0.1578(3) 0.0179(10) Uani 1 1 d . . . H6 H 0.5468 -0.0003 0.1726 0.021 Uiso 1 1 calc R . . C7 C 0.3726(8) 0.1250(3) 0.0638(3) 0.0195(10) Uani 1 1 d . . . H7 H 0.4814 0.1130 0.0141 0.023 Uiso 1 1 calc R . . N8 N 0.2975(6) 0.0160(3) 0.3268(2) 0.0119(7) Uani 1 1 d . . . C9 C 0.5013(10) 0.0461(5) 0.4047(4) 0.0137(12) Uani 1 1 d . . . C10 C 0.4895(7) -0.0327(3) 0.4997(3) 0.0116(9) Uani 1 1 d . . . H10 H 0.6198 -0.0997 0.5015 0.014 Uiso 1 1 calc R . . C11 C 0.2315(7) -0.0973(3) 0.4749(3) 0.0164(10) Uani 1 1 d . . . H11A H 0.2486 -0.1892 0.4843 0.020 Uiso 1 1 calc R . . H11B H 0.1166 -0.0653 0.5210 0.020 Uiso 1 1 calc R . . C12 C 0.1345(8) -0.0657(3) 0.3635(3) 0.0117(9) Uani 1 1 d . . . O13 O 0.6578(5) 0.1244(2) 0.39145(19) 0.0208(7) Uani 1 1 d . . . O14 O -0.0590(5) -0.1028(2) 0.30970(19) 0.0176(7) Uani 1 1 d . . . C15 C 0.5588(9) 0.0459(4) 0.5983(4) 0.0128(12) Uani 1 1 d . . . H15 H 0.7181 0.0896 0.5900 0.015 Uiso 1 1 calc R . . C16 C 0.3669(8) 0.1495(3) 0.5999(3) 0.0131(9) Uani 1 1 d . . . O17 O 0.1956(5) 0.1680(2) 0.5280(2) 0.0299(8) Uani 1 1 d . . . O18 O 0.4111(5) 0.2240(3) 0.6812(2) 0.0277(8) Uani 1 1 d . . . H18 H 0.3012 0.2804 0.6760 0.042 Uiso 1 1 calc R . . C19 C 0.6218(7) -0.0307(3) 0.6998(3) 0.0142(9) Uani 1 1 d . . . H19 H 0.7331 -0.1010 0.6847 0.017 Uiso 1 1 calc R . . C20 C 0.7702(11) 0.0449(5) 0.7895(4) 0.0251(15) Uani 1 1 d . . . H20A H 0.6598 0.1071 0.8141 0.038 Uiso 1 1 calc R . . H20B H 0.9103 0.0877 0.7649 0.038 Uiso 1 1 calc R . . H20C H 0.8354 -0.0119 0.8467 0.038 Uiso 1 1 calc R . . C21 C 0.3922(8) -0.0908(4) 0.7346(3) 0.0242(11) Uani 1 1 d . . . H21A H 0.4449 -0.1399 0.7980 0.036 Uiso 1 1 calc R . . H21B H 0.3089 -0.1459 0.6793 0.036 Uiso 1 1 calc R . . H21C H 0.2754 -0.0250 0.7487 0.036 Uiso 1 1 calc R . . # Atomic displacement parameters with standard deviations 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 Br1 0.0346(2) 0.0284(2) 0.01686(18) 0.0065(4) 0.00100(17) -0.0092(4) C2 0.025(3) 0.013(2) 0.018(2) 0.0072(19) 0.003(2) -0.006(2) C3 0.022(3) 0.012(2) 0.016(2) 0.0043(19) -0.003(2) -0.001(2) C4 0.017(2) 0.015(2) 0.013(2) -0.0007(18) 0.009(2) -0.003(2) C5 0.011(3) 0.011(3) 0.009(3) 0.001(2) 0.000(2) -0.004(2) C6 0.014(2) 0.020(2) 0.020(2) -0.0021(19) 0.002(2) 0.001(2) C7 0.021(2) 0.027(2) 0.013(2) -0.005(2) 0.009(2) 0.002(2) N8 0.0105(19) 0.0107(17) 0.0157(19) -0.0009(15) 0.0056(16) 0.0015(15) C9 0.012(3) 0.015(3) 0.014(3) -0.009(2) 0.001(2) 0.004(2) C10 0.009(2) 0.0069(19) 0.019(2) -0.0024(18) 0.0016(18) -0.0006(18) C11 0.021(3) 0.013(2) 0.016(2) -0.0007(18) 0.006(2) 0.001(2) C12 0.017(2) 0.009(2) 0.009(2) -0.0062(17) 0.004(2) 0.0032(19) O13 0.0190(17) 0.0242(16) 0.0197(17) 0.0017(13) 0.0050(15) -0.0104(15) O14 0.0175(16) 0.0209(16) 0.0134(15) -0.0005(12) -0.0003(14) -0.0091(14) C15 0.007(3) 0.015(3) 0.017(3) 0.002(2) 0.002(2) 0.001(2) C16 0.010(2) 0.012(2) 0.019(3) -0.0033(19) 0.009(2) -0.002(2) O17 0.0242(19) 0.0263(18) 0.0336(19) -0.0085(15) -0.0120(16) 0.0128(15) O18 0.034(2) 0.0247(17) 0.0218(16) -0.0141(14) -0.0021(16) 0.0193(15) C19 0.017(2) 0.014(2) 0.012(2) 0.0014(18) 0.002(2) 0.0023(19) C20 0.036(4) 0.024(3) 0.013(3) -0.001(2) -0.002(3) 0.004(3) C21 0.035(3) 0.020(2) 0.016(2) 0.0015(19) -0.002(2) -0.009(2) # Bond lengths (in Angstroms) with standard deviations 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 Br1 C2 1.904(4) . ? C2 C7 1.343(5) . ? C2 C3 1.391(5) . ? C3 C4 1.384(4) . ? C3 H3 0.9500 . ? C4 C5 1.365(5) . ? C4 H4 0.9500 . ? C5 C6 1.392(6) . ? C5 N8 1.428(5) . ? C6 C7 1.403(5) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? N8 C12 1.377(5) . ? N8 C9 1.408(6) . ? C9 O13 1.220(5) . ? C9 C10 1.504(6) . ? C10 C15 1.528(5) . ? C10 C11 1.541(5) . ? C10 H10 1.0000 . ? C11 C12 1.498(5) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 O14 1.226(4) . ? C15 C16 1.517(6) . ? C15 C19 1.542(6) . ? C15 H15 1.0000 . ? C16 O17 1.221(4) . ? C16 O18 1.314(4) . ? O18 H18 0.8400 . ? C19 C21 1.527(5) . ? C19 C20 1.534(5) . ? C19 H19 1.0000 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? # Bond angles with standard deviations 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 C7 C2 C3 121.8(4) . . ? C7 C2 Br1 120.8(3) . . ? C3 C2 Br1 117.3(3) . . ? C4 C3 C2 118.9(4) . . ? C4 C3 H3 120.6 . . ? C2 C3 H3 120.6 . . ? C5 C4 C3 119.6(4) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? C4 C5 C6 121.5(4) . . ? C4 C5 N8 120.2(4) . . ? C6 C5 N8 118.2(4) . . ? C5 C6 C7 118.1(4) . . ? C5 C6 H6 121.0 . . ? C7 C6 H6 121.0 . . ? C2 C7 C6 120.0(4) . . ? C2 C7 H7 120.0 . . ? C6 C7 H7 120.0 . . ? C12 N8 C9 111.3(3) . . ? C12 N8 C5 124.8(4) . . ? C9 N8 C5 123.2(4) . . ? O13 C9 N8 122.2(4) . . ? O13 C9 C10 128.3(4) . . ? N8 C9 C10 109.4(4) . . ? C9 C10 C15 110.3(3) . . ? C9 C10 C11 103.5(3) . . ? C15 C10 C11 120.8(3) . . ? C9 C10 H10 107.2 . . ? C15 C10 H10 107.2 . . ? C11 C10 H10 107.2 . . ? C12 C11 C10 105.4(3) . . ? C12 C11 H11A 110.7 . . ? C10 C11 H11A 110.7 . . ? C12 C11 H11B 110.7 . . ? C10 C11 H11B 110.7 . . ? H11A C11 H11B 108.8 . . ? O14 C12 N8 122.7(3) . . ? O14 C12 C11 127.8(4) . . ? N8 C12 C11 109.5(3) . . ? C16 C15 C10 109.6(4) . . ? C16 C15 C19 115.6(4) . . ? C10 C15 C19 114.8(3) . . ? C16 C15 H15 105.3 . . ? C10 C15 H15 105.3 . . ? C19 C15 H15 105.3 . . ? O17 C16 O18 122.5(4) . . ? O17 C16 C15 122.9(4) . . ? O18 C16 C15 114.5(4) . . ? C16 O18 H18 109.5 . . ? C21 C19 C20 110.2(3) . . ? C21 C19 C15 113.4(3) . . ? C20 C19 C15 112.9(4) . . ? C21 C19 H19 106.6 . . ? C20 C19 H19 106.6 . . ? C15 C19 H19 106.6 . . ? 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 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? # Torsion angles with standard deviations 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 C7 C2 C3 C4 0.8(6) . . . . ? Br1 C2 C3 C4 -177.2(3) . . . . ? C2 C3 C4 C5 1.1(5) . . . . ? C3 C4 C5 C6 -2.6(6) . . . . ? C3 C4 C5 N8 176.0(4) . . . . ? C4 C5 C6 C7 2.2(6) . . . . ? N8 C5 C6 C7 -176.4(4) . . . . ? C3 C2 C7 C6 -1.2(6) . . . . ? Br1 C2 C7 C6 176.8(3) . . . . ? C5 C6 C7 C2 -0.3(6) . . . . ? C4 C5 N8 C12 60.9(5) . . . . ? C6 C5 N8 C12 -120.5(4) . . . . ? C4 C5 N8 C9 -108.5(5) . . . . ? C6 C5 N8 C9 70.1(5) . . . . ? C12 N8 C9 O13 -174.2(4) . . . . ? C5 N8 C9 O13 -3.5(6) . . . . ? C12 N8 C9 C10 6.4(4) . . . . ? C5 N8 C9 C10 177.1(4) . . . . ? O13 C9 C10 C15 41.2(6) . . . . ? N8 C9 C10 C15 -139.4(3) . . . . ? O13 C9 C10 C11 171.8(5) . . . . ? N8 C9 C10 C11 -8.9(4) . . . . ? C9 C10 C11 C12 8.0(4) . . . . ? C15 C10 C11 C12 131.9(3) . . . . ? C9 N8 C12 O14 178.5(4) . . . . ? C5 N8 C12 O14 8.0(6) . . . . ? C9 N8 C12 C11 -0.9(4) . . . . ? C5 N8 C12 C11 -171.4(4) . . . . ? C10 C11 C12 O14 175.9(4) . . . . ? C10 C11 C12 N8 -4.8(4) . . . . ? C9 C10 C15 C16 63.6(5) . . . . ? C11 C10 C15 C16 -57.1(5) . . . . ? C9 C10 C15 C19 -164.5(3) . . . . ? C11 C10 C15 C19 74.9(5) . . . . ? C10 C15 C16 O17 -4.1(6) . . . . ? C19 C15 C16 O17 -135.6(4) . . . . ? C10 C15 C16 O18 -179.1(3) . . . . ? C19 C15 C16 O18 49.4(5) . . . . ? C16 C15 C19 C21 56.4(5) . . . . ? C10 C15 C19 C21 -72.7(4) . . . . ? C16 C15 C19 C20 -69.9(5) . . . . ? C10 C15 C19 C20 161.1(4) . . . . ? # absolute configuration determined by X-rays _chemical_absolute_configuration ad _refine_ls_abs_structure_Flack 0.031(13) _refine_ls_abs_structure_details '(Flack, 1983)' #################################################### _publ_section_references ; Bergerhoff, G. (1996). DIAMOND (Version 1.2). Gerhard-Domagk Str. 1, D-53121 Bonn, Germany. Flack, H.D. (1983). Acta Cryst. A39, 876-881 Sheldrick, G.M. (1997). SHELXS97 and SHELXL97, University of G\"ottingen, Germany. Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13. ; _symmetry_cell_setting monoclinic _cell_measurement_temperature 100(1) _cell_measurement_reflns_used 1425 _cell_measurement_theta_min 3.7001 _cell_measurement_theta_max 32.1179 _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.05 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.823 _exptl_absorpt_correction_T_max 0.870 _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _diffrn_measurement_device_type 'Xcalibur-3 kappa-diffractometer with Sapphire-III CCD' _diffrn_measurement_method '\w scans at different \f' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_detector_area_resol_mean 16.5467 _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_molecular_graphics 'DIAMOND (Bergerhoff, 1996)' _computing_publication_material 'Platon (Spek, 2003); SHELXL97' _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _diffrn_reflns_number 7190 _diffrn_reflns_av_R_equivalents 0.0786 _exptl_crystal_F_000 360 _exptl_absorpt_coefficient_mu 2.795 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.70 _diffrn_reflns_theta_max 32.17 _reflns_number_total 3064 _reflns_number_gt 1436 _reflns_threshold_expression I>2\s(I) _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0040P)^2^] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 3064 _refine_ls_number_parameters 194 _refine_ls_number_restraints 1 _refine_ls_goodness_of_fit_ref 0.669 _refine_ls_restrained_S_all 0.669 _diffrn_measured_fraction_theta_max 0.925 _diffrn_reflns_theta_full 32.17 _diffrn_measured_fraction_theta_full 0.925 _refine_diff_density_max 0.390 _refine_diff_density_min -0.450 _refine_diff_density_rms 0.086 _refine_ls_structure_factor_coef Fsqd