Enantioselective reduction of azaarene-based ketones via visible light-driven photoredox asymmetric catalysis
Qiao, Baokun; Li, Chunyang; Zhao, Xiaowei; Yin, Yanli; Jiang, Zhiyong; Chemical Communications  (2019) –; doi:10.1039/C9CC03661J

data_7123588
_publ_section_title
;
 Enantioselective reduction of azaarene-based ketones via visible
 light-driven photoredox asymmetric catalysis
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03661J
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H14 Cl N O'
_chemical_formula_sum            'C20 H14 Cl N O'
_chemical_formula_weight         319.77
_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             2019-05-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-02 deposited with the CCDC.    2019-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.15285(17)
_cell_length_b                   11.3914(5)
_cell_length_c                   26.4345(10)
_cell_measurement_reflns_used    2520
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.4810
_cell_measurement_theta_min      4.2080
_cell_volume                     1551.66(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega -104.00  -11.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -37.0000 -180.0000 186

  2 omega  -71.00   39.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   19.0000  -60.0000 220

  3 omega  -52.00   35.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000  -30.0000 174

  4 omega   59.00  111.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  178.0000  -90.0000 104

  5 omega   43.00   89.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437 -122.0000  -43.0000 92

  6 omega    9.00   41.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  -37.0000    0.0000 64

  7 omega   70.00  105.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437   37.0000    0.0000 70

  8 omega   18.00   59.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437   37.0000    0.0000 82

  9 omega  -24.00    3.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  -37.0000    0.0000 54

 10 omega   60.00   96.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  178.0000   60.0000 72

 11 omega  -33.00    8.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  -19.0000   90.0000 82

 12 omega   14.00   41.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  -19.0000   90.0000 54

 13 omega   39.00   66.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437   57.0000 -120.0000 54

 14 omega   61.00   89.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437   37.0000   90.0000 56

 15 omega    2.00   75.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437   19.0000  -60.0000 146

 16 omega   76.00  103.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  178.0000 -150.0000 54

 17 omega   60.00  111.00   0.5000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       36.5437  178.0000  150.0000 102

 18 omega   38.00   83.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 90

 19 omega   44.00   73.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 58

 20 omega  101.00  178.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 154

 21 omega   38.00  106.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 136

 22 omega   44.00  114.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 140

 23 omega  122.00  149.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000    0.0000 54

 24 omega   50.00   90.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000    0.0000 80

 25 omega   38.00   69.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   30.0000 62

 26 omega   50.00  116.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 132

 27 omega   77.00  115.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 76

 28 omega   37.00   84.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 94

 29 omega   40.00   67.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 54

 30 omega   38.00   75.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 74

 31 omega   43.00   70.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 54

 32 omega   40.00  116.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000 -150.0000 152

 33 omega   40.00   87.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 94

 34 omega   56.00  120.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -129.0000   51.0000 128

 35 omega   48.00  153.00   0.5000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000  150.0000 210
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0307330000
_diffrn_orient_matrix_UB_12      0.1344111000
_diffrn_orient_matrix_UB_13      0.0023159000
_diffrn_orient_matrix_UB_21      0.0088966000
_diffrn_orient_matrix_UB_22      -0.0058278000
_diffrn_orient_matrix_UB_23      0.0581849000
_diffrn_orient_matrix_UB_31      0.2973518000
_diffrn_orient_matrix_UB_32      -0.0136424000
_diffrn_orient_matrix_UB_33      -0.0019913000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0644
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            10220
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.055
_diffrn_reflns_theta_max         67.055
_diffrn_reflns_theta_min         4.226
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.197
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       needle
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 760 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.026(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         2755
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0669
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1207P)^2^+0.1395P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1777
_refine_ls_wR_factor_ref         0.1906
_reflns_Friedel_coverage         0.674
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2331
_reflns_number_total             2755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03661j2.cif
_cod_data_source_block           qbk4cl
_cod_database_code               7123588
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4Cl1
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.734
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13),
 C17(H17), C18(H18), C19(H19), C20(H20)
2.c Fitted hexagon refined as free rotating group:
 C14(C9,C10,C11,C12,C13)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1A)
;
_olex2_submission_special_instructions 'No special instructions were received'