Pyridine-N-oxide catalyzed asymmetric N-acylative desymmetrization of sulfonimidamides
Guo, Cui-Mei; Zhang, Fang-Yuan; Tian, Yin; Xie, Ming-Sheng; Guo, Hai-Ming; Chemical Science 16 (2025) 8812–8819; doi:10.1039/D5SC01270H

data_1574374
_publ_section_title
;
 Pyridine-N-oxide catalyzed asymmetric N-acylative desymmetrization of
 sulfonimidamides
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              8812
_journal_page_last               8819
_journal_paper_doi               10.1039/D5SC01270H
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H20 N2 O4 S'
_chemical_formula_sum            'C17 H20 N2 O4 S'
_chemical_formula_weight         348.41
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-11-13
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-11-13 deposited with the CCDC.	2025-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.504(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   4.99040(10)
_cell_length_b                   10.6896(2)
_cell_length_c                   16.6446(3)
_cell_measurement_reflns_used    12461
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7820
_cell_measurement_theta_min      4.9230
_cell_volume                     885.17(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_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 0.995
_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    -65.00  32.00   1.00    3.03    --  -35.62  81.00 -22.00   97
  2  \w    -21.00  65.00   1.00    3.03    --   35.62 -81.00-145.00   86
  3  \w    103.00 175.00   1.00   12.12    --  106.81  81.00 -22.00   72
  4  \w     39.00 136.00   1.00   12.12    --  106.81 -81.00-145.00   97
  5  \w    -52.00  32.00   1.00    3.03    --  -35.62  57.00  60.00   84
  6  \w   -108.00 -37.00   1.00    3.03    --  -35.62 178.00-180.00   71
  7  \w     19.00 103.00   1.00    3.03    --   35.62  57.00 -90.00   84
  8  \w     17.00 105.00   1.00    3.03    --   35.62  38.00  90.00   88
  9  \w      6.00 107.00   1.00    3.03    --   35.62  19.00  90.00  101
 10  \w     58.00 108.00   1.00    3.03    --   35.62-178.00-180.00   50
 11  \w     61.00 108.00   1.00    3.03    --   35.62 178.00-120.00   47
 12  \w    104.00 174.00   1.00   12.12    --  106.81 111.00 150.00   70
 13  \w     85.00 177.00   1.00   12.12    --  106.81  30.00  30.00   92
 14  \w     89.00 174.00   1.00   12.12    --  106.81  61.00  90.00   85
 15  \w     89.00 175.00   1.00   12.12    --  106.81  45.00  90.00   86
 16  \w     40.00 108.00   1.00   12.12    --  106.81-111.00-180.00   68
 17  \w     89.00 175.00   1.00   12.12    --  106.81  45.00  60.00   86
 18  \w    103.00 174.00   1.00   12.12    --  106.81  77.00-150.00   71
 19  \w     61.00 146.00   1.00   12.12    --  106.81 178.00  90.00   85
 20  \w     38.00 124.00   1.00   12.12    --  106.81 -45.00-180.00   86
 21  \w     89.00 175.00   1.00   12.12    --  106.81  45.00 120.00   86
 22  \w     89.00 174.00   1.00   12.12    --  106.81  61.00-120.00   85
 23  \w     89.00 174.00   1.00   12.12    --  106.81  61.00 -60.00   85
 24  \w     40.00 108.00   1.00   12.12    --  106.81-111.00-150.00   68
 25  \w     89.00 174.00   1.00   12.12    --  106.81  61.00  60.00   85
 26  \w     89.00 174.00   1.00   12.12    --  106.81  61.00 -90.00   85
 27  \w   -103.00 -19.00   1.00    3.03    --  -35.62 -57.00 -30.00   84
 28  \w     19.00 103.00   1.00    3.03    --   35.62  57.00 120.00   84
 29  \w     19.00 103.00   1.00    3.03    --   35.62  57.00 -30.00   84
 30  \w     19.00 103.00   1.00    3.03    --   35.62  57.00-180.00   84
 31  \w      6.00  74.00   1.00    3.03    --   35.62 -99.00-180.00   68
 32  \w    -34.00  55.00   1.00    3.03    --   35.62 -38.00  90.00   89
 33  \w     19.00 103.00   1.00    3.03    --   35.62  57.00  90.00   84
 34  \w     19.00 103.00   1.00    3.03    --   35.62  57.00-150.00   84
 35  \w     89.00 175.00   1.00   12.12    --  106.81  45.00 -90.00   86
 36  \w     89.00 175.00   1.00   12.12    --  106.81  45.00 -60.00   86
 37  \w     85.00 177.00   1.00   12.12    --  106.81  30.00   0.00   92
 38  \w     89.00 175.00   1.00   12.12    --  106.81  45.00 150.00   86
 39  \w     89.00 174.00   1.00   12.12    --  106.81  61.00-150.00   85
 40  \w     89.00 175.00   1.00   12.12    --  106.81  45.00-150.00   86
 41  \w     85.00 177.00   1.00   12.12    --  106.81  30.00 -90.00   92
 42  \w     37.00 106.00   1.00   12.12    --  106.81 -94.00  60.00   69
 43  \w     68.00 178.00   1.00   12.12    --  106.81  15.00   0.00  110
 44  \w     85.00 177.00   1.00   12.12    --  106.81  30.00-180.00   92
 45  \w     89.00 175.00   1.00   12.12    --  106.81  45.00-180.00   86
 46  \w     85.00 177.00   1.00   12.12    --  106.81  30.00 150.00   92
 47  \w     89.00 174.00   1.00   12.12    --  106.81  61.00  30.00   85
 48  \w     89.00 174.00   1.00   12.12    --  106.81  61.00 150.00   85
 49  \w     89.00 175.00   1.00   12.12    --  106.81  45.00  30.00   86
 50  \w     40.00 108.00   1.00   12.12    --  106.81-111.00 150.00   68
 51  \w   -103.00 -19.00   1.00    3.03    --  -35.62 -57.00 -90.00   84
 52  \w   -108.00 -39.00   1.00    3.03    --  -35.62-178.00-150.00   69
 53  \w      6.00  74.00   1.00    3.03    --   35.62 -99.00 -30.00   68
 54  \w     19.00 103.00   1.00    3.03    --   35.62  57.00  60.00   84
 55  \w     19.00 103.00   1.00    3.03    --   35.62  57.00  30.00   84
 56  \w     19.00 103.00   1.00    3.03    --   35.62  57.00 150.00   84
 57  \w     17.00 105.00   1.00    3.03    --   35.62  38.00 -90.00   88
 58  \w     17.00 105.00   1.00    3.03    --   35.62  38.00 120.00   88
 59  \w     89.00 174.00   1.00   12.12    --  106.81  61.00 120.00   85
 60  \w     89.00 174.00   1.00   12.12    --  106.81  61.00   0.00   85
 61  \w     85.00 177.00   1.00   12.12    --  106.81  30.00 120.00   92
 62  \w     40.00 108.00   1.00   12.12    --  106.81-111.00 120.00   68
 63  \w     89.00 175.00   1.00   12.12    --  106.81  45.00   0.00   86
 64  \w     89.00 175.00   1.00   12.12    --  106.81  45.00-120.00   86
 65  \w     89.00 174.00   1.00   12.12    --  106.81  61.00-180.00   85
 66  \w     85.00 136.00   1.00   12.12    --  106.81  30.00  60.00   51
 67  \w     89.00 175.00   1.00   12.12    --  106.81  45.00 -30.00   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      -0.1864284000
_diffrn_orient_matrix_UB_12      -0.0103389000
_diffrn_orient_matrix_UB_13      0.0691922000
_diffrn_orient_matrix_UB_21      0.1111389000
_diffrn_orient_matrix_UB_22      0.1247413000
_diffrn_orient_matrix_UB_23      0.0349795000
_diffrn_orient_matrix_UB_31      -0.2208897000
_diffrn_orient_matrix_UB_32      0.0713992000
_diffrn_orient_matrix_UB_33      -0.0510929000
_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  0.0696
_diffrn_reflns_av_unetI/netI     0.0410
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22527
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.414
_diffrn_reflns_theta_min         4.921
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.824
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44108
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             368
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.341
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1396 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.035(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         3402
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0768P)^2^+0.1251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1220
_reflns_Friedel_coverage         0.884
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                3210
_reflns_number_total             3402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01270h2.cif
_cod_data_source_block           gcm-20241111
_cod_depositor_comments          'Adding full bibliography for 1574374.cif.'
_cod_database_code               1574374
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.825
_shelx_estimated_absorpt_t_min   0.771
_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 C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C5(H5), C6(H6), C11(H11), C12(H12), C14(H14), C15(H15)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              52533
_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 2.169
_oxdiff_exptl_absorpt_empirical_full_min 0.425