Redox Deracemization of Tertiary Stereocenters Adjacent to an Electron-Withdrawing Group
Mao, Ying; Wang, Zehua; Wang, Gang; Zhao, Ran; Kan, Linglong; Pan, Xiaoguang; Liu, Lei; ACS Catalysis  (2020) 7785–7791; doi:10.1021/acscatal.0c02486

data_4517829
_publ_section_title
;
 Redox Deracemization of Tertiary Stereocenters Adjacent to an
 Electron-Withdrawing Group
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              7785
_journal_page_last               7791
_journal_paper_doi               10.1021/acscatal.0c02486
_journal_year                    2020
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C15 H13 N O'
_chemical_formula_sum            'C15 H13 N O'
_chemical_formula_weight         223.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.652(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.6989(2)
_cell_length_b                   5.6085(2)
_cell_length_c                   13.5280(4)
_cell_measurement_reflns_used    5588
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.4260
_cell_measurement_theta_min      3.2230
_cell_volume                     583.50(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -90.00 -63.00   1.00    0.10    --  -48.45 -15.00  -3.00   27
  2  \w      5.00  30.00   1.00    0.10    --   48.45 -15.00  -3.00   25
  3  \w     59.00  97.00   1.00    0.10    --   48.45  15.00 166.00   38
  4  \w    -87.00 -55.00   1.00    0.40    --  -86.25  15.00 166.00   32
  5  \w   -118.00 -90.00   1.00    0.40    --  -86.25 -15.00  -3.00   28
  6  \w     60.00 102.00   1.00    0.40    --  106.49 -15.00  -3.00   42
  7  \w    142.00 168.00   1.00    0.40    --  106.49  15.00 166.00   26
  8  \w     95.00 139.00   1.00    0.40    --  106.49  15.00 166.00   44
  9  \w    -55.00 -26.00   1.00    0.10    --  -48.45 -77.00 -90.00   29
 10  \w    -66.00 -12.00   1.00    0.10    --  -48.45 125.00-120.00   54
 11  \w    -80.00 -36.00   1.00    0.10    --  -48.45 -19.00-120.00   44
 12  \w    -60.00 -28.00   1.00    0.10    --  -48.45 -77.00 -30.00   32
 13  \w    -70.00 -33.00   1.00    0.10    --  -48.45 -77.00-180.00   37
 14  \w    -53.00 -28.00   1.00    0.10    --  -48.45 -77.00-120.00   25
 15  \w    -42.00 -16.00   1.00    0.10    --  -48.45  15.00 166.00   26
 16  \w    -59.00 -34.00   1.00    0.10    --  -48.45 -77.00-150.00   25
 17  \w     42.00  67.00   1.00    0.10    --   48.45  37.00 -90.00   25
 18  \w    -77.00 -15.00   1.00    0.40    --  -86.25  61.00-120.00   62
 19  \w    -87.00 -62.00   1.00    0.40    --  -86.25 -79.00 -55.92   25
 20  \w   -117.00 -74.00   1.00    0.40    --  -86.25 -61.00 -60.00   43
 21  \w    -47.00 -13.00   1.00    0.40    --  -86.25  77.00  30.00   34
 22  \w    -88.00 -62.00   1.00    0.40    --  -86.25 -81.00 -71.32   26
 23  \w   -155.00 -73.00   1.00    0.40    --  -86.25 -61.00 -90.00   82
 24  \w    -96.00 -65.00   1.00    0.40    --  -86.25 -81.00-100.72   31
 25  \w    -95.00 -70.00   1.00    0.40    --  -86.25 -59.00 -47.05   25
 26  \w   -123.00 -65.00   1.00    0.40    --  -86.25 -72.00-136.57   58
 27  \w    -89.00 -64.00   1.00    0.40    --  -86.25 -75.00 -55.24   25
 28  \w    -88.00 -63.00   1.00    0.40    --  -86.25 -77.00 -30.00   25
 29  \w    -88.00 -63.00   1.00    0.40    --  -86.25 -77.00 -90.00   25
 30  \w    -97.00 -72.00   1.00    0.40    --  -86.25 -55.00 -48.69   25
 31  \w   -116.00 -65.00   1.00    0.40    --  -86.25 -72.00-149.76   51
 32  \w    -89.00 -64.00   1.00    0.40    --  -86.25 -77.00-120.00   25
 33  \w    -89.00 -64.00   1.00    0.40    --  -86.25 -77.00-150.00   25
 34  \w   -113.00 -63.00   1.00    0.40    --  -86.25 -80.00 -93.54   50
 35  \w    110.00 135.00   1.00    0.40    --  106.49  45.00 -30.00   25
 36  \w     50.00  99.00   1.00    0.40    --  106.49 -94.00-180.00   49
 37  \w     37.00 107.00   1.00    0.40    --  106.49 -94.00 120.00   70
 38  \w     35.00 113.00   1.00    0.40    --  106.49 -61.00  60.00   78
 39  \w    101.00 126.00   1.00    0.40    --  106.49  61.00-120.00   25
 40  \w    110.00 171.00   1.00    0.40    --  106.49  77.00 -30.00   61
 41  \w     54.00 108.00   1.00    0.40    --  106.49 -94.00   0.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0356842000
_diffrn_orient_matrix_UB_12      -0.0079829000
_diffrn_orient_matrix_UB_13      -0.1110179000
_diffrn_orient_matrix_UB_21      -0.1933152000
_diffrn_orient_matrix_UB_22      -0.0556023000
_diffrn_orient_matrix_UB_23      -0.0244699000
_diffrn_orient_matrix_UB_31      -0.0389156000
_diffrn_orient_matrix_UB_32      0.2688278000
_diffrn_orient_matrix_UB_33      -0.0082955000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0338
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6647
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         3.270
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             236
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.120
_refine_diff_density_min         -0.138
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 837 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.02(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2043
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0475P)^2^+0.0743P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0843
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                1975
_reflns_number_total             2043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02486_si_002.cif
_cod_data_source_block           190415c
_cod_depositor_comments          'Adding full bibliography for 4517829.cif.'
_cod_database_code               4517829
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         CNO
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.969
_reflns_odcompleteness_completeness 99.91
_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 C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              75622
_shelx_hkl_checksum              79448
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.524
_oxdiff_exptl_absorpt_empirical_full_min 0.691