Organic base-promoted enantioselective electrophilic cyanation of β-keto esters by using chiral phase-transfer catalysts.
Chen, Min; Huang, Zhi-Tang; Zheng, Qi-Yu; Organic & biomolecular chemistry 13 (2015) 8812–8816; doi:10.1039/c5ob01301a

data_7154623
_publ_section_title
;
 Organic base-promoted enantioselective electrophilic cyanation of \b-keto
 esters by using chiral phase-transfer catalysts.
;
_journal_issue                   33
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8812
_journal_page_last               8816
_journal_paper_doi               10.1039/c5ob01301a
_journal_volume                  13
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H20 Br N O3'
_chemical_formula_sum            'C21 H20 Br N O3'
_chemical_formula_weight         414.29
_chemical_name_systematic        sa3912
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.12 svn.r3133 for OlexSys, GUI svn.r4987)
;
_audit_update_record
;
2015-04-08 deposited with the CCDC.
2015-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4981(19)
_cell_length_b                   11.985(4)
_cell_length_c                   23.813(7)
_cell_measurement_reflns_used    5710
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4819
_cell_measurement_theta_min      1.7103
_cell_volume                     1854.5(10)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 18.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.0722
              2theta: -20.0213
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 18.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.0722
              2theta: -20.0213
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0055
_diffrn_orient_matrix_UB_12      0.0803
_diffrn_orient_matrix_UB_13      0.1311
_diffrn_orient_matrix_UB_21      0.0599
_diffrn_orient_matrix_UB_22      -0.0484
_diffrn_orient_matrix_UB_23      0.0322
_diffrn_orient_matrix_UB_31      0.0292
_diffrn_orient_matrix_UB_32      0.0262
_diffrn_orient_matrix_UB_33      -0.0149
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            14635
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         3.078
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.237
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.484
_exptl_crystal_description       plate
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 1416 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         4250
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0407
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0205P)^2^+0.8832P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0733
_refine_ls_wR_factor_ref         0.0747
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4035
_reflns_number_total             4250
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ob01301a2.cif
_cod_data_source_block           sa3912
_cod_depositor_comments          'Adding full bibliography for 7154623.cif.'
_cod_original_cell_volume        1854.6(9)
_cod_database_code               7154623
_diffrn_number_total             2483
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C16(H16), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C13(H13A,H13B), C15(H15A,H15B), C17(H17A,H17B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7)
;
_shelx_res_checksum              13014
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'