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_4518829
_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         'Cl, C22 H29 N4 O2'
_chemical_formula_sum            'C22 H29 Cl N4 O2'
_chemical_formula_weight         416.94
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.90840(10)
_cell_length_b                   11.7353(2)
_cell_length_c                   16.7685(2)
_cell_measurement_reflns_used    21359
_cell_measurement_temperature    297
_cell_measurement_theta_max      71.3850
_cell_measurement_theta_min      3.7720
_cell_volume                     2146.59(5)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      297
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -82.00   9.00   1.00    1.00    --  -35.62 112.00 -88.00   91
  2  \w     14.00 106.00   1.00    1.00    --   35.62  30.00  64.00   92
  3  \w     37.00 129.00   1.00    1.00    --  107.12 -30.00 -96.00   92
  4  \w     37.00 111.00   1.00    1.00    --  107.12 -98.00  77.00   74
  5  \w    101.00 177.00   1.00    1.00    --  107.12 112.00 -88.00   76
  6  \w   -103.00 -19.00   1.00    1.00    --  -35.62 -57.00 120.00   84
  7  \w     55.00 108.00   1.00    1.00    --   35.62-178.00-150.00   53
  8  \w      0.00  74.00   1.00    1.00    --   35.62 -98.00  77.00   74
  9  \w     40.00 125.00   1.00    1.00    --  107.12 -61.00 -30.00   85
 10  \w     38.00 110.00   1.00    1.00    --  107.12 -95.00 -30.00   72
 11  \w    100.00 177.00   1.00    1.00    --  107.12 111.00   0.00   77
 12  \w     38.00 110.00   1.00    1.00    --  107.12 -95.00-180.00   72
 13  \w     40.00 125.00   1.00    1.00    --  107.12 -61.00-150.00   85
 14  \w     37.00 129.00   1.00    1.00    --  107.12 -30.00  30.00   92
 15  \w   -103.00 -19.00   1.00    1.00    --  -35.62 -57.00 -60.00   84
 16  \w   -103.00  -9.00   1.00    1.00    --  -35.62 -77.00-120.00   94
 17  \w      9.00 103.00   1.00    1.00    --   35.62  77.00  60.00   94
 18  \w     57.00 108.00   1.00    1.00    --   35.62 178.00 -60.00   51
 19  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 -30.00   95
 20  \w     86.00 177.00   1.00    1.00    --  107.12  30.00   0.00   91
 21  \w     69.00 178.00   1.00    1.00    --  107.12  15.00 -90.00  109
 22  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  60.00   95
 23  \w     69.00 178.00   1.00    1.00    --  107.12  15.00  90.00  109
 24  \w     80.00 175.00   1.00    1.00    --  107.12  77.00-180.00   95
 25  \w     90.00 176.00   1.00    1.00    --  107.12  45.00 -60.00   86
 26  \w     69.00 178.00   1.00    1.00    --  107.12  15.00-180.00  109
 27  \w      9.00 103.00   1.00    1.00    --   35.62  77.00-180.00   94
 28  \w    -34.00  55.00   1.00    1.00    --   35.62 -38.00-150.00   89
 29  \w    -34.00  55.00   1.00    1.00    --   35.62 -38.00 -30.00   89
 30  \w    -36.00  65.00   1.00    1.00    --   35.62 -19.00  60.00  101
 31  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  90.00   95
 32  \w     80.00 175.00   1.00    1.00    --  107.12  77.00   0.00   95
 33  \w     80.00 175.00   1.00    1.00    --  107.12  77.00-120.00   95
 34  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  30.00   95
 35  \w     80.00 144.00   1.00    1.00    --  107.12  77.00 -60.00   64
 36  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 150.00   95
;
_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      0.0952877000
_diffrn_orient_matrix_UB_12      0.0471789000
_diffrn_orient_matrix_UB_13      -0.0592384000
_diffrn_orient_matrix_UB_21      0.1008393000
_diffrn_orient_matrix_UB_22      -0.0125870000
_diffrn_orient_matrix_UB_23      0.0637321000
_diffrn_orient_matrix_UB_31      0.0264131000
_diffrn_orient_matrix_UB_32      -0.1218570000
_diffrn_orient_matrix_UB_33      -0.0294803000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0790
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            30789
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.299
_diffrn_reflns_theta_min         4.599
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.777
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46817
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.247
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1667 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(8)
_refine_ls_extinction_coef       0.0152(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         4170
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0683P)^2^+0.1663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1045
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.754
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4033
_reflns_number_total             4170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01438_si_003.cif
_cod_data_source_block           ln-20200909
_cod_depositor_comments
'Adding full bibliography for 4518829--4518831.cif.'
_cod_database_code               4518829
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_reflns_odcompleteness_completeness 99.95
_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, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(H18C)=Sof(H18D)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=1-FVAR(1)
 Sof(H18A)=Sof(H18B)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C4(H4), C10(H10)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B), C18(H18A,
 H18B), C18(H18C,H18D), C21(H21A,H21B), C21(H21C,H21D), C22(H22A,H22B),
 C22A(H22C,H22D)
3.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C14(H14), C16(H16), C19(H19), C20(H20)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              28265
_shelx_hkl_checksum              54833
_olex2_date_sample_data_collection 2020-09-09
_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 2.762
_oxdiff_exptl_absorpt_empirical_full_min 0.632