Dynamic Kinetic Resolution of Carboxylic Esters Catalyzed by Chiral PPY N-Oxides: Synthesis of Nonsteroidal Anti-Inflammatory Drugs and Mechanistic Insights
Xie, Ming-Sheng; Li, Ning; Tian, Yin; Wu, Xiao-Xia; Deng, Yun; Qu, Gui-Rong; Guo, Hai-Ming; ACS Catalysis 11 (2021) 8183–8196; doi:10.1021/acscatal.1c01438

data_4518830
_publ_section_title
;
 Dynamic Kinetic Resolution of Carboxylic Esters Catalyzed by Chiral PPY
 N-Oxides: Synthesis of Nonsteroidal Anti-Inflammatory Drugs and
 Mechanistic Insights
;
_journal_issue                   13
_journal_name_full               'ACS Catalysis'
_journal_page_first              8183
_journal_page_last               8196
_journal_paper_doi               10.1021/acscatal.1c01438
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H22 Cl N3 O2, H2 O'
_chemical_formula_sum            'C23 H24 Cl N3 O3'
_chemical_formula_weight         425.90
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.28930(10)
_cell_length_b                   19.28930(10)
_cell_length_c                   6.05040(10)
_cell_measurement_reflns_used    17218
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.2870
_cell_measurement_theta_min      4.5590
_cell_volume                     2251.22(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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   -104.00 -18.00   1.00    1.96    --  -35.62 -42.00-170.00   86
  2  \w    -53.00  33.00   1.00    1.96    --  -35.62  42.00 -18.00   86
  3  \w   -104.00 -50.00   1.00    1.96    --  -35.62-159.00 -33.00   54
  4  \w     18.00 104.00   1.00    1.96    --   35.62  42.00 -18.00   86
  5  \w    -33.00  53.00   1.00    1.96    --   35.62 -42.00-170.00   86
  6  \w     71.00 165.00   1.00    7.82    --  107.12 159.00  -1.00   94
  7  \w     38.00 125.00   1.00    7.82    --  107.12 -42.00-170.00   87
  8  \w     38.00 114.00   1.00    7.82    --  107.12-118.00 119.00   76
  9  \w     89.00 176.00   1.00    7.82    --  107.12  42.00 -18.00   87
 10  \w     98.00 177.00   1.00    7.82    --  107.12 118.00-154.00   79
 11  \w    100.00 175.00   1.00    7.82    --  107.12  80.00 129.00   75
 12  \w     57.00 108.00   1.00    1.96    --   35.62 178.00-120.00   51
 13  \w     18.00  85.00   1.00    1.96    --   35.62-118.00 119.00   67
 14  \w     19.00 103.00   1.00    1.96    --   35.62  57.00  90.00   84
 15  \w     -1.00  25.00   1.00    1.96    --   35.62  95.00  -9.40   26
 16  \w     38.00 110.00   1.00    7.82    --  107.12 -95.00 -90.00   72
 17  \w     89.00 174.00   1.00    7.82    --  107.12  61.00  90.00   85
 18  \w     38.00 110.00   1.00    7.82    --  107.12 -95.00-180.00   72
 19  \w     90.00 176.00   1.00    7.82    --  107.12  45.00  60.00   86
 20  \w     40.00 125.00   1.00    7.82    --  107.12 -61.00 120.00   85
 21  \w     86.00 177.00   1.00    7.82    --  107.12  30.00 120.00   91
 22  \w     90.00 176.00   1.00    7.82    --  107.12  45.00  90.00   86
 23  \w     80.00 175.00   1.00    7.82    --  107.12  77.00  90.00   95
 24  \w     89.00 176.00   1.00    7.82    --  107.12  42.00  47.81   87
 25  \w     89.00 174.00   1.00    7.82    --  107.12  61.00  60.00   85
 26  \w     80.00 175.00   1.00    7.82    --  107.12  77.00  60.00   95
 27  \w     86.00 177.00   1.00    7.82    --  107.12  30.00  90.00   91
 28  \w   -105.00 -17.00   1.00    1.96    --  -35.62 -38.00 -30.00   88
 29  \w      9.00 103.00   1.00    1.96    --   35.62  77.00 120.00   94
 30  \w      9.00 103.00   1.00    1.96    --   35.62  77.00 -30.00   94
 31  \w     57.00 108.00   1.00    1.96    --   35.62 178.00 120.00   51
 32  \w      9.00 103.00   1.00    1.96    --   35.62  77.00-180.00   94
 33  \w     57.00 108.00   1.00    1.96    --   35.62 178.00 -90.00   51
 34  \w     42.00 108.00   1.00    1.96    --   35.62-159.00 -33.00   66
 35  \w      9.00 103.00   1.00    1.96    --   35.62  77.00 -90.00   94
 36  \w     80.00 175.00   1.00    7.82    --  107.12  77.00 150.00   95
 37  \w     89.00 174.00   1.00    7.82    --  107.12  61.00 -60.00   85
 38  \w     90.00 176.00   1.00    7.82    --  107.12  45.00-120.00   86
 39  \w     80.00 175.00   1.00    7.82    --  107.12  77.00-180.00   95
 40  \w     90.00 176.00   1.00    7.82    --  107.12  45.00 -90.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0252107000
_diffrn_orient_matrix_UB_12      0.0757042000
_diffrn_orient_matrix_UB_13      0.0114674000
_diffrn_orient_matrix_UB_21      -0.0635541000
_diffrn_orient_matrix_UB_22      -0.0231880000
_diffrn_orient_matrix_UB_23      0.1353449000
_diffrn_orient_matrix_UB_31      0.0412796000
_diffrn_orient_matrix_UB_32      0.0105049000
_diffrn_orient_matrix_UB_33      0.2153472000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            33973
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.591
_diffrn_reflns_theta_min         4.585
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.733
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.03452
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.257
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.136
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1612 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4287
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0363
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0622P)^2^+0.1317P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.950
_reflns_Friedel_fraction_max     0.942
_reflns_number_gt                3992
_reflns_number_total             4287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01438_si_004.cif
_cod_data_source_block           ln-20201029
_cod_depositor_comments
'Adding full bibliography for 4518829--4518831.cif.'
_cod_database_code               4518830
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 O1 N1 Cl1'
_shelx_estimated_absorpt_t_max   0.746
_shelx_estimated_absorpt_t_min   0.607
_diffrn_oxdiff_digest_frames
;
01b39a73a32b3baf7cf27d43a71b6751f300033bf48
;
_diffrn_oxdiff_digest_hkl
;
01a9a5b51024eabe0d508103870455773d9fd0
;
_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, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2.a Free rotating group:
 O1(H1A,H1B)
2.b Ternary CH refined with riding coordinates:
 C7(H7), C15(H15)
2.c Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C16(H16A,H16B), C17(H17A,H17B)
2.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C8(H8), C4(H4), C10(H10), C23(H23), C5(H5), C9(H9), C1(H1),
 C11(H11), C22(H22), C2(H2), C3(H3A)
;
_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 4.727
_oxdiff_exptl_absorpt_empirical_full_min 0.443