data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Ya-Wen Zhang' _publ_contact_author_email ZHANGYW@SUDA.EDU.CN _publ_section_title ; Highly Diastereo- and enantioselective organocatalytic addition of acetone to ?-substituted ?-ketoesters via dynamic kinetic resolution ; loop_ _publ_author_name 'Ya-Wen Zhang' 'Zhenhua Ding' 'Zongxuan Shen' 'Ting Wang' 'Jin Yang' # Attachment 'shelxl.cif' data_shelxl _database_code_depnum_ccdc_archive 'CCDC 701396' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H19 Br O5' _chemical_formula_sum 'C16 H19 Br O5' _chemical_formula_weight 371.22 _chemical_absolute_configuration ad 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' 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 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' _symmetry_Int_Tables_number 19 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' _cell_length_a 9.6480(19) _cell_length_b 9.9528(19) _cell_length_c 17.941(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1722.8(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5460 _cell_measurement_theta_min 3.1 _cell_measurement_theta_max 25.3 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.57 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.431 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 760 _exptl_absorpt_coefficient_mu 2.405 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.323 _exptl_absorpt_correction_T_max 0.485 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 7.31 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16895 _diffrn_reflns_av_R_equivalents 0.0531 _diffrn_reflns_av_sigmaI/netI 0.0441 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.06 _diffrn_reflns_theta_max 25.34 _reflns_number_total 3146 _reflns_number_gt 2208 _reflns_threshold_expression >2sigma(I) _computing_data_collection CrystalClear _computing_cell_refinement CrystalClear _computing_data_reduction CrystalStructure _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0549P)^2^+0.7152P] 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 SHELXL _refine_ls_extinction_coef 0.0033(12) _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 0.03(2) _refine_ls_number_reflns 3146 _refine_ls_number_parameters 200 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.1148 _refine_ls_R_factor_gt 0.0748 _refine_ls_wR_factor_ref 0.1602 _refine_ls_wR_factor_gt 0.1449 _refine_ls_goodness_of_fit_ref 1.169 _refine_ls_restrained_S_all 1.194 _refine_ls_shift/su_max 0.000 _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 Br1 Br 0.69922(12) 0.71278(13) 0.59608(5) 0.1465(6) Uani 1 1 d . . . O1 O 0.6199(7) 1.0137(4) 0.2603(3) 0.1044(17) Uani 1 1 d . . . O2 O 0.6189(5) 0.9356(4) 0.1089(2) 0.0818(12) Uani 1 1 d . . . H2 H 0.6517 0.9931 0.1365 0.123 Uiso 1 1 calc R . . O3 O 0.8604(6) 0.8698(6) 0.1718(4) 0.130(2) Uani 1 1 d . . . O4 O 0.7934(5) 0.6564(6) 0.1888(3) 0.1102(18) Uani 1 1 d D . . O5 O 0.7786(6) 0.7296(7) 0.0167(3) 0.136(2) Uani 1 1 d . . . C1 C 0.6218(6) 0.8469(5) 0.3515(3) 0.0595(14) Uani 1 1 d . . . C2 C 0.5792(6) 0.7218(6) 0.3762(3) 0.0689(16) Uani 1 1 d . . . H2A H 0.5358 0.6632 0.3433 0.083 Uiso 1 1 calc R . . C3 C 0.6005(7) 0.6830(7) 0.4491(3) 0.0807(18) Uani 1 1 d . . . H3 H 0.5688 0.6000 0.4656 0.097 Uiso 1 1 calc R . . C4 C 0.6685(7) 0.7672(8) 0.4968(3) 0.0821(19) Uani 1 1 d . . . C5 C 0.7144(8) 0.8901(8) 0.4746(4) 0.092(2) Uani 1 1 d . . . H5 H 0.7604 0.9467 0.5076 0.110 Uiso 1 1 calc R . . C6 C 0.6907(6) 0.9286(6) 0.4017(4) 0.0752(16) Uani 1 1 d . . . H6 H 0.7222 1.0121 0.3858 0.090 Uiso 1 1 calc R . . C7 C 0.5953(7) 0.8958(6) 0.2746(3) 0.0702(16) Uani 1 1 d . . . C8 C 0.5384(6) 0.8034(6) 0.2158(3) 0.0598(14) Uani 1 1 d . . . H8 H 0.5411 0.7114 0.2352 0.072 Uiso 1 1 calc R . . C9 C 0.6275(6) 0.8087(6) 0.1438(3) 0.0613(14) Uani 1 1 d . . . C10 C 0.7761(7) 0.7830(8) 0.1680(4) 0.086(2) Uani 1 1 d . . . C11 C 0.9437(17) 0.630(2) 0.1977(12) 0.130(5) Uiso 0.50 1 d PD . . H11A H 0.9999 0.7006 0.1755 0.155 Uiso 0.50 1 calc PR . . H11B H 0.9706 0.5437 0.1775 0.155 Uiso 0.50 1 calc PR . . C11' C 0.9122(17) 0.612(2) 0.2356(11) 0.130(5) Uiso 0.50 1 d PD . . H11C H 0.8889 0.5298 0.2619 0.155 Uiso 0.50 1 calc PR . . H11D H 0.9350 0.6804 0.2721 0.155 Uiso 0.50 1 calc PR . . C12 C 0.950(3) 0.633(3) 0.2807(12) 0.172(7) Uiso 0.50 1 d PD . . H12A H 1.0443 0.6245 0.2967 0.258 Uiso 0.50 1 calc PR . . H12B H 0.8966 0.5591 0.3003 0.258 Uiso 0.50 1 calc PR . . H12C H 0.9120 0.7159 0.2987 0.258 Uiso 0.50 1 calc PR . . C12' C 1.033(2) 0.588(3) 0.1844(12) 0.172(7) Uiso 0.50 1 d PD . . H12D H 1.1106 0.5562 0.2127 0.258 Uiso 0.50 1 calc PR . . H12E H 1.0574 0.6711 0.1602 0.258 Uiso 0.50 1 calc PR . . H12F H 1.0080 0.5228 0.1475 0.258 Uiso 0.50 1 calc PR . . C13 C 0.3858(6) 0.8412(6) 0.2014(4) 0.0755(18) Uani 1 1 d . . . H13A H 0.3344 0.8339 0.2471 0.113 Uiso 1 1 calc R . . H13B H 0.3472 0.7815 0.1650 0.113 Uiso 1 1 calc R . . H13C H 0.3809 0.9319 0.1834 0.113 Uiso 1 1 calc R . . C14 C 0.5755(5) 0.7054(6) 0.0886(3) 0.0659(14) Uani 1 1 d . . . H14A H 0.5618 0.6214 0.1150 0.079 Uiso 1 1 calc R . . H14B H 0.4856 0.7345 0.0706 0.079 Uiso 1 1 calc R . . C15 C 0.6659(7) 0.6787(7) 0.0229(4) 0.0806(18) Uani 1 1 d . . . C16 C 0.6118(9) 0.5833(9) -0.0339(4) 0.112(3) Uani 1 1 d . . . H16A H 0.6796 0.5715 -0.0725 0.169 Uiso 1 1 calc R . . H16B H 0.5280 0.6187 -0.0551 0.169 Uiso 1 1 calc R . . H16C H 0.5928 0.4983 -0.0107 0.169 Uiso 1 1 calc R . . 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 0.1672(10) 0.2064(11) 0.0659(5) 0.0253(6) -0.0327(5) -0.0469(8) O1 0.165(5) 0.055(3) 0.094(4) 0.002(2) -0.021(3) -0.013(3) O2 0.103(3) 0.068(2) 0.074(3) 0.018(2) 0.011(3) -0.005(2) O3 0.075(3) 0.101(4) 0.214(7) -0.037(4) -0.011(4) -0.020(3) O4 0.066(3) 0.098(4) 0.167(5) 0.005(3) -0.040(3) 0.010(3) O5 0.101(4) 0.174(6) 0.134(5) -0.052(4) 0.058(4) -0.038(4) C1 0.067(3) 0.050(3) 0.062(3) -0.004(3) -0.008(3) 0.013(3) C2 0.079(4) 0.072(4) 0.055(3) -0.004(3) -0.008(3) -0.002(3) C3 0.090(4) 0.086(5) 0.066(4) 0.012(4) -0.009(4) -0.014(4) C4 0.084(4) 0.106(5) 0.056(3) 0.002(4) -0.019(3) -0.004(4) C5 0.108(5) 0.095(5) 0.071(4) -0.018(4) -0.023(4) -0.011(5) C6 0.087(4) 0.062(4) 0.077(4) -0.009(4) -0.019(4) -0.009(3) C7 0.086(4) 0.057(4) 0.068(4) 0.001(3) -0.002(3) 0.009(3) C8 0.077(4) 0.053(3) 0.049(3) 0.001(3) -0.004(3) -0.004(3) C9 0.060(3) 0.057(3) 0.067(3) -0.001(3) 0.005(3) -0.003(3) C10 0.062(4) 0.082(5) 0.114(5) -0.023(5) -0.012(4) 0.000(4) C13 0.073(4) 0.082(4) 0.071(4) 0.008(3) 0.015(3) 0.010(4) C14 0.058(3) 0.083(4) 0.056(3) -0.005(3) 0.004(3) -0.001(3) C15 0.069(4) 0.100(5) 0.074(4) -0.002(4) 0.016(3) 0.000(4) C16 0.112(6) 0.146(7) 0.079(5) -0.035(5) 0.020(4) 0.003(6) _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 Br1 C4 1.885(6) . ? O1 C7 1.224(7) . ? O2 C9 1.412(6) . ? O2 H2 0.8200 . ? O3 C10 1.188(8) . ? O4 C10 1.325(9) . ? O4 C11 1.482(15) . ? O4 C11' 1.489(15) . ? O5 C15 1.204(8) . ? C1 C6 1.383(8) . ? C1 C2 1.384(8) . ? C1 C7 1.486(8) . ? C2 C3 1.378(8) . ? C2 H2A 0.9300 . ? C3 C4 1.367(9) . ? C3 H3 0.9300 . ? C4 C5 1.360(9) . ? C5 C6 1.383(9) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 C8 1.504(8) . ? C8 C13 1.541(8) . ? C8 C9 1.552(7) . ? C8 H8 0.9800 . ? C9 C14 1.513(8) . ? C9 C10 1.519(9) . ? C11 C12 1.492(17) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C11' C12' 1.502(18) . ? C11' H11C 0.9700 . ? C11' H11D 0.9700 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? C12' H12D 0.9600 . ? C12' H12E 0.9600 . ? C12' H12F 0.9600 . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 C15 1.491(8) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 C16 1.487(10) . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? 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 C9 O2 H2 109.5 . . ? C10 O4 C11 108.7(11) . . ? C10 O4 C11' 122.6(11) . . ? C11 O4 C11' 30.0(10) . . ? C6 C1 C2 117.6(5) . . ? C6 C1 C7 119.6(5) . . ? C2 C1 C7 122.8(5) . . ? C3 C2 C1 120.7(6) . . ? C3 C2 H2A 119.6 . . ? C1 C2 H2A 119.6 . . ? C4 C3 C2 119.6(6) . . ? C4 C3 H3 120.2 . . ? C2 C3 H3 120.2 . . ? C5 C4 C3 121.6(6) . . ? C5 C4 Br1 118.9(5) . . ? C3 C4 Br1 119.4(5) . . ? C4 C5 C6 118.2(6) . . ? C4 C5 H5 120.9 . . ? C6 C5 H5 120.9 . . ? C1 C6 C5 122.2(6) . . ? C1 C6 H6 118.9 . . ? C5 C6 H6 118.9 . . ? O1 C7 C1 118.4(6) . . ? O1 C7 C8 120.6(5) . . ? C1 C7 C8 121.0(5) . . ? C7 C8 C13 108.4(5) . . ? C7 C8 C9 111.2(5) . . ? C13 C8 C9 112.5(5) . . ? C7 C8 H8 108.2 . . ? C13 C8 H8 108.2 . . ? C9 C8 H8 108.2 . . ? O2 C9 C14 107.4(5) . . ? O2 C9 C10 109.4(5) . . ? C14 C9 C10 112.7(5) . . ? O2 C9 C8 111.5(4) . . ? C14 C9 C8 109.7(4) . . ? C10 C9 C8 106.2(5) . . ? O3 C10 O4 126.0(7) . . ? O3 C10 C9 122.7(7) . . ? O4 C10 C9 111.1(6) . . ? O4 C11 C12 98.2(16) . . ? O4 C11 H11A 112.1 . . ? C12 C11 H11A 112.1 . . ? O4 C11 H11B 112.1 . . ? C12 C11 H11B 112.1 . . ? H11A C11 H11B 109.8 . . ? O4 C11' C12' 107.3(17) . . ? O4 C11' H11C 110.2 . . ? C12' C11' H11C 110.2 . . ? O4 C11' H11D 110.2 . . ? C12' C11' H11D 110.2 . . ? H11C C11' H11D 108.5 . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C11' C12' H12D 109.5 . . ? C11' C12' H12E 109.5 . . ? H12D C12' H12E 109.5 . . ? C11' C12' H12F 109.5 . . ? H12D C12' H12F 109.5 . . ? H12E C12' H12F 109.5 . . ? C8 C13 H13A 109.5 . . ? C8 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C8 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C15 C14 C9 116.4(5) . . ? C15 C14 H14A 108.2 . . ? C9 C14 H14A 108.2 . . ? C15 C14 H14B 108.2 . . ? C9 C14 H14B 108.2 . . ? H14A C14 H14B 107.3 . . ? O5 C15 C16 121.5(6) . . ? O5 C15 C14 121.8(6) . . ? C16 C15 C14 116.8(6) . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 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 C6 C1 C2 C3 2.5(9) . . . . ? C7 C1 C2 C3 -177.0(6) . . . . ? C1 C2 C3 C4 -2.2(10) . . . . ? C2 C3 C4 C5 1.0(11) . . . . ? C2 C3 C4 Br1 -179.3(5) . . . . ? C3 C4 C5 C6 -0.1(11) . . . . ? Br1 C4 C5 C6 -179.9(5) . . . . ? C2 C1 C6 C5 -1.6(9) . . . . ? C7 C1 C6 C5 177.9(6) . . . . ? C4 C5 C6 C1 0.5(11) . . . . ? C6 C1 C7 O1 -9.0(9) . . . . ? C2 C1 C7 O1 170.5(6) . . . . ? C6 C1 C7 C8 171.5(5) . . . . ? C2 C1 C7 C8 -9.0(9) . . . . ? O1 C7 C8 C13 -72.6(8) . . . . ? C1 C7 C8 C13 106.9(6) . . . . ? O1 C7 C8 C9 51.5(8) . . . . ? C1 C7 C8 C9 -129.0(6) . . . . ? C7 C8 C9 O2 -66.4(6) . . . . ? C13 C8 C9 O2 55.4(6) . . . . ? C7 C8 C9 C14 174.7(5) . . . . ? C13 C8 C9 C14 -63.4(6) . . . . ? C7 C8 C9 C10 52.7(6) . . . . ? C13 C8 C9 C10 174.5(5) . . . . ? C11 O4 C10 O3 -15.7(14) . . . . ? C11' O4 C10 O3 14.0(16) . . . . ? C11 O4 C10 C9 169.2(10) . . . . ? C11' O4 C10 C9 -161.2(11) . . . . ? O2 C9 C10 O3 15.7(9) . . . . ? C14 C9 C10 O3 135.2(7) . . . . ? C8 C9 C10 O3 -104.7(8) . . . . ? O2 C9 C10 O4 -168.9(6) . . . . ? C14 C9 C10 O4 -49.5(8) . . . . ? C8 C9 C10 O4 70.7(7) . . . . ? C10 O4 C11 C12 103.9(15) . . . . ? C11' O4 C11 C12 -20(3) . . . . ? C10 O4 C11' C12' -83.8(18) . . . . ? C11 O4 C11' C12' -14(2) . . . . ? O2 C9 C14 C15 70.2(6) . . . . ? C10 C9 C14 C15 -50.4(7) . . . . ? C8 C9 C14 C15 -168.5(5) . . . . ? C9 C14 C15 O5 5.0(10) . . . . ? C9 C14 C15 C16 -176.5(6) . . . . ? 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 O2 H2 O1 0.82 2.25 2.824(7) 127.4 . C5 H5 O2 0.93 2.46 3.376(8) 170.5 4_675 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.34 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.234 _refine_diff_density_min -0.287 _refine_diff_density_rms 0.042