Chiral 4-Aryl-pyridine-N-oxide Nucleophilic Catalysts: Design, Synthesis, and Application in Acylative Dynamic Kinetic Resolution
Xie, Ming-Sheng; Shan, Meng; Li, Ning; Chen, Yang-Guang; Wang, Xiao-Bing; Cheng, Xuan; Tian, Yin; Wu, Xiao-Xia; Deng, Yun; Qu, Gui-Rong; Guo, Hai-Ming; ACS Catalysis  (2021) 877–891; doi:10.1021/acscatal.1c04923

data_4519237
_publ_section_title
;
 Chiral 4-Aryl-pyridine-N-oxide Nucleophilic Catalysts: Design, Synthesis,
 and Application in Acylative Dynamic Kinetic Resolution
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              877
_journal_page_last               891
_journal_paper_doi               10.1021/acscatal.1c04923
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H37 N3 O2'
_chemical_formula_sum            'C30 H37 N3 O2'
_chemical_formula_weight         471.62
_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
_audit_creation_date             2018-12-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2240(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.54630(10)
_cell_length_b                   9.24720(10)
_cell_length_c                   12.84270(10)
_cell_measurement_reflns_used    26263
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8940
_cell_measurement_theta_min      5.0020
_cell_volume                     1369.06(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_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    -54.00  34.00   1.00    2.44    --  -35.37  38.00 -30.00   88
  2  \w    -54.00  34.00   1.00    2.44    --  -35.37  38.00   0.00   88
  3  \w   -107.00  -6.00   1.00    2.44    --  -35.37 -20.00 151.00  101
  4  \w     23.00  89.00   1.00    2.44    --   35.37-125.00 -90.00   66
  5  \w      9.00 103.00   1.00    2.44    --   35.37  77.00  60.00   94
  6  \w      9.00 103.00   1.00    2.44    --   35.37  77.00  30.00   94
  7  \w      9.00 103.00   1.00    2.44    --   35.37  77.00 -60.00   94
  8  \w     16.00 105.00   1.00    2.44    --   35.37  38.00  60.00   89
  9  \w     23.00  89.00   1.00    2.44    --   35.37-125.00  60.00   66
 10  \w     19.00 103.00   1.00    2.44    --   35.37  57.00  30.00   84
 11  \w     19.00 103.00   1.00    2.44    --   35.37  57.00-150.00   84
 12  \w     80.00 174.00   1.00    9.78    --  106.50  77.00 -30.00   94
 13  \w     88.00 173.00   1.00    9.78    --  106.50  61.00  60.00   85
 14  \w     80.00 174.00   1.00    9.78    --  106.50  77.00  60.00   94
 15  \w     88.00 173.00   1.00    9.78    --  106.50  61.00  30.00   85
 16  \w     80.00 174.00   1.00    9.78    --  106.50  77.00  30.00   94
 17  \w     88.00 173.00   1.00    9.78    --  106.50  61.00  90.00   85
 18  \w     85.00 176.00   1.00    9.78    --  106.50  30.00 150.00   91
 19  \w     85.00 176.00   1.00    9.78    --  106.50  30.00  90.00   91
 20  \w     37.00 112.00   1.00    9.78    --  106.50-111.00 -30.00   75
 21  \w     89.00 175.00   1.00    9.78    --  106.50  45.00  90.00   86
 22  \w     85.00 176.00   1.00    9.78    --  106.50  30.00   0.00   91
 23  \w     85.00 176.00   1.00    9.78    --  106.50  30.00 120.00   91
 24  \w     37.00 109.00   1.00    9.78    --  106.50 -95.00   0.00   72
 25  \w     88.00 173.00   1.00    9.78    --  106.50  61.00   0.00   85
 26  \w     37.00 109.00   1.00    9.78    --  106.50 -95.00-180.00   72
 27  \w     85.00 176.00   1.00    9.78    --  106.50  30.00  30.00   91
 28  \w     80.00 174.00   1.00    9.78    --  106.50  77.00   0.00   94
 29  \w     88.00 173.00   1.00    9.78    --  106.50  61.00 120.00   85
 30  \w     80.00 174.00   1.00    9.78    --  106.50  77.00  90.00   94
 31  \w     85.00 176.00   1.00    9.78    --  106.50  30.00  60.00   91
 32  \w     88.00 173.00   1.00    9.78    --  106.50  61.00 -30.00   85
 33  \w     89.00 175.00   1.00    9.78    --  106.50  45.00   0.00   86
 34  \w     89.00 175.00   1.00    9.78    --  106.50  45.00  60.00   86
 35  \w     80.00 174.00   1.00    9.78    --  106.50  77.00 120.00   94
 36  \w     39.00 133.00   1.00    9.78    --  106.50 -77.00-150.00   94
 37  \w    -36.00  65.00   1.00    2.44    --   35.37 -19.00  30.00  101
 38  \w      6.00 107.00   1.00    2.44    --   35.37  19.00 -30.00  101
 39  \w    -34.00  54.00   1.00    2.44    --   35.37 -38.00 150.00   88
 40  \w    -32.00  52.00   1.00    2.44    --   35.37 -57.00  30.00   84
 41  \w    -32.00  52.00   1.00    2.44    --   35.37 -57.00  90.00   84
 42  \w      9.00 103.00   1.00    2.44    --   35.37  77.00 120.00   94
 43  \w     19.00 103.00   1.00    2.44    --   35.37  57.00 -90.00   84
 44  \w      1.00  74.00   1.00    2.44    --   35.37 -99.00 120.00   73
 45  \w      9.00 103.00   1.00    2.44    --   35.37  77.00-150.00   94
 46  \w     16.00 105.00   1.00    2.44    --   35.37  38.00 120.00   89
 47  \w      9.00 103.00   1.00    2.44    --   35.37  77.00 -90.00   94
 48  \w     88.00 173.00   1.00    9.78    --  106.50  61.00 -60.00   85
 49  \w     80.00 174.00   1.00    9.78    --  106.50  77.00-180.00   94
 50  \w     37.00 109.00   1.00    9.78    --  106.50 -95.00  90.00   72
 51  \w     80.00 174.00   1.00    9.78    --  106.50  77.00 -90.00   94
 52  \w     80.00 174.00   1.00    9.78    --  106.50  77.00-150.00   94
 53  \w     88.00 173.00   1.00    9.78    --  106.50  61.00 150.00   85
 54  \w     89.00 175.00   1.00    9.78    --  106.50  45.00-120.00   86
 55  \w     88.00 173.00   1.00    9.78    --  106.50  61.00 -90.00   85
 56  \w     39.00 133.00   1.00    9.78    --  106.50 -77.00  30.00   94
 57  \w     85.00 176.00   1.00    9.78    --  106.50  30.00-150.00   91
 58  \w     85.00 176.00   1.00    9.78    --  106.50  30.00 -30.00   91
 59  \w     88.00 173.00   1.00    9.78    --  106.50  61.00-150.00   85
 60  \w     80.00 174.00   1.00    9.78    --  106.50  77.00 -60.00   94
 61  \w     88.00 173.00   1.00    9.78    --  106.50  61.00-120.00   85
 62  \w     88.00 173.00   1.00    9.78    --  106.50  61.00-180.00   85
 63  \w     80.00 174.00   1.00    9.78    --  106.50  77.00-120.00   94
 64  \w     85.00 176.00   1.00    9.78    --  106.50  30.00-120.00   91
 65  \w     85.00 176.00   1.00    9.78    --  106.50  30.00 -60.00   91
 66  \w     85.00 176.00   1.00    9.78    --  106.50  30.00-180.00   91
 67  \w     89.00 175.00   1.00    9.78    --  106.50  45.00-150.00   86
 68  \w     85.00 176.00   1.00    9.78    --  106.50  30.00 -90.00   91
 69  \w     80.00 174.00   1.00    9.78    --  106.50  77.00 150.00   94
 70  \w   -103.00 -19.00   1.00    2.44    --  -35.37 -57.00-150.00   84
 71  \w   -104.00 -18.00   1.00    2.44    --  -35.37 -42.00-140.12   86
 72  \w   -103.00 -19.00   1.00    2.44    --  -35.37 -57.00 150.00   84
 73  \w     19.00 103.00   1.00    2.44    --   35.37  57.00 -60.00   84
 74  \w    -34.00 105.00   1.00    2.44    --   35.37   0.00-150.00  139
 75  \w    -34.00 105.00   1.00    2.44    --   35.37   0.00-180.00  139
 76  \w      1.00  74.00   1.00    2.44    --   35.37 -99.00-120.00   73
 77  \w    -34.00 105.00   1.00    2.44    --   35.37   0.00 -90.00  139
 78  \w    -34.00 105.00   1.00    2.44    --   35.37   0.00-120.00  139
 79  \w      9.00 103.00   1.00    2.44    --   35.37  77.00-180.00   94
 80  \w     19.00 103.00   1.00    2.44    --   35.37  57.00 120.00   84
 81  \w     68.00 178.00   1.00    9.78    --  106.50  15.00 -90.00  110
 82  \w     89.00 175.00   1.00    9.78    --  106.50  45.00 -60.00   86
 83  \w     68.00 178.00   1.00    9.78    --  106.50  15.00 -30.00  110
 84  \w     89.00 175.00   1.00    9.78    --  106.50  45.00 150.00   86
 85  \w     37.00 150.00   1.00    9.78    --  106.50   0.00   0.00  113
 86  \w     37.00 176.00   1.00    9.78    --  106.50   0.00 -30.00  139
 87  \w     37.00 176.00   1.00    9.78    --  106.50   0.00 -60.00  139
 88  \w     37.00 176.00   1.00    9.78    --  106.50   0.00 -90.00  139
 89  \w     37.00 176.00   1.00    9.78    --  106.50   0.00-120.00  139
 90  \w     37.00 176.00   1.00    9.78    --  106.50   0.00-150.00  139
 91  \w     37.00 176.00   1.00    9.78    --  106.50   0.00-180.00  139
;
_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      -0.1219195000
_diffrn_orient_matrix_UB_12      -0.0183953000
_diffrn_orient_matrix_UB_13      -0.0534346000
_diffrn_orient_matrix_UB_21      0.0546697000
_diffrn_orient_matrix_UB_22      -0.0366541000
_diffrn_orient_matrix_UB_23      -0.1034874000
_diffrn_orient_matrix_UB_31      0.0014748000
_diffrn_orient_matrix_UB_32      -0.1614647000
_diffrn_orient_matrix_UB_33      0.0295554000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            55113
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.390
_diffrn_reflns_theta_min         3.447
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.562
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42709
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.144
_exptl_crystal_description       plate
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.126
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1617 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.284
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         4806
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.284
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0303P)^2^+0.5510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1339
_reflns_Friedel_coverage         0.694
_reflns_Friedel_fraction_full    0.800
_reflns_Friedel_fraction_max     0.789
_reflns_number_gt                4304
_reflns_number_total             4806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04923_si_002.cif
_cod_data_source_block           sm-20181226
_cod_database_code               4519237
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.786
_reflns_odcompleteness_completeness 100.00
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C33(H33), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 N14(H14), C6(H6), C4(H4), C20(H20), C3(H3), C18(H18), C26(H26), C16(H16),
 C28(H28), C27(H27)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C22(H22A,H22B,H22C), C34(H34A,H34B,H34C), C21(H21A,H21B,
 H21C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              99823
_shelx_hkl_checksum              12048
_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 1.630
_oxdiff_exptl_absorpt_empirical_full_min 0.536