Ligand-controlled divergent enantioselective hydroarylation of cyclobutenes.
Pan, Renming; Zhu, Jie; Zhou, Xinjie; Wang, Minyan; Lu, Ping; Chemical science 16 (2025) 21498–21507; doi:10.1039/d5sc05740j

data_1576019
_publ_section_title
;
 Ligand-controlled divergent enantioselective hydroarylation of
 cyclobutenes.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              21498
_journal_page_last               21507
_journal_paper_doi               10.1039/d5sc05740j
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H19 N O2'
_chemical_formula_sum            'C23 H19 N O2'
_chemical_formula_weight         341.39
_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             2023-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-04-03 deposited with the CCDC.	2025-10-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.27240(10)
_cell_length_b                   12.61370(10)
_cell_length_c                   22.6390(3)
_cell_measurement_reflns_used    22456
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      74.3550
_cell_measurement_theta_min      3.8820
_cell_volume                     1791.16(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -15.00  31.00   1.00    1.00    --    0.00  27.00 -41.00   46
  2  \w    -76.00 -49.00   1.00    1.00    --    0.00 -27.00 155.00   27
  3  \w      6.00 115.00   1.00    1.00    --   95.80 -27.00 155.00  109
  4  \w     76.00 117.00   1.00    1.00    --   95.80  27.00 -41.00   41
  5  \w     46.00  82.00   1.00    1.00    --    0.00  77.00   0.00   36
  6  \w     52.00  89.00   1.00    1.00    --    0.00  57.00 -90.00   37
  7  \w     26.00  88.00   1.00    1.00    --    0.00  57.00  60.00   62
  8  \w    -17.00  82.00   1.00    1.00    --    0.00  57.00   0.00   99
  9  \w    -10.00  19.00   1.00    1.00    --    0.00  77.00   0.00   29
 10  \w    -22.00  81.00   1.00    1.00    --    0.00  57.00 150.00  103
 11  \w     32.00  68.00   1.00    1.00    --    0.00  37.00   0.00   36
 12  \w     -9.00  18.00   1.00    1.00    --    0.00  37.00   0.00   27
 13  \w    -23.00  22.00   1.00    1.00    --    0.00  57.00  60.00   45
 14  \w    -27.00  19.00   1.00    1.00    --    0.00 -27.00 155.00   46
 15  \w    -23.00   3.00   1.00    1.00    --    0.00  57.00 -90.00   26
 16  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 17  \w     34.00 127.00   1.00    1.00    --   95.80 -82.00 -30.00   93
 18  \w     65.00  91.00   1.00    1.00    --   95.80  82.00 -30.00   26
 19  \w    116.00 185.00   1.00    1.00    --   95.80  67.00 106.90   69
 20  \w     69.00  94.00   1.00    1.00    --   95.80  67.00 106.90   25
 21  \w     65.00 159.00   1.00    1.00    --   95.80  77.00 120.00   94
 22  \w    155.00 181.00   1.00    1.00    --   95.80  82.00-150.00   26
 23  \w     63.00 108.00   1.00    1.00    --   95.80  82.00-120.00   45
 24  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 25  \w    131.00 172.00   1.00    1.00    --   95.80  75.00 171.01   41
 26  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 27  \w    120.00 153.00   1.00    1.00    --   95.80  45.00 -30.00   33
 28  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 29  \w     76.00 119.00   1.00    1.00    --   95.80  45.00  60.00   43
 30  \w    122.00 160.00   1.00    1.00    --   95.80  45.00  60.00   38
 31  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   26
 32  \w     69.00 104.00   1.00    1.00    --   95.80  65.00 -80.86   35
 33  \w     72.00 110.00   1.00    1.00    --   95.80  56.00 -14.41   38
 34  \w    147.00 172.00   1.00    1.00    --   95.80  56.00 -14.41   25
 35  \w     66.00  92.00   1.00    1.00    --   95.80  75.00 171.01   26
 36  \w     69.00 184.00   1.00    1.00    --   95.80  66.00-163.84  115
 37  \w     27.00 128.00   1.00    1.00    --   95.80 -82.00 120.00  101
 38  \w     38.00 128.00   1.00    1.00    --   95.80 -82.00 -90.00   90
 39  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 40  \w     64.00  90.00   1.00    1.00    --   95.80  82.00-180.00   26
 41  \w    118.00 184.00   1.00    1.00    --   95.80  82.00 -90.00   66
 42  \w    139.00 165.00   1.00    1.00    --   95.80  77.00 150.00   26
 43  \w     72.00 140.00   1.00    1.00    --   95.80  57.00   0.34   68
 44  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 45  \w     64.00  90.00   1.00    1.00    --   95.80  82.00 -90.00   26
 46  \w     71.00 104.00   1.00    1.00    --   95.80  61.00  60.00   33
 47  \w    128.00 154.00   1.00    1.00    --   95.80  61.00  60.00   26
 48  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 49  \w    122.00 147.00   1.00    1.00    --   95.80  77.00  30.00   25
 50  \w     75.00 112.00   1.00    1.00    --   95.80  45.00 -30.00   37
 51  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 52  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 53  \w     34.00 123.00   1.00    1.00    --   95.80 -82.00-180.00   89
 54  \w     71.00 180.00   1.00    1.00    --   95.80  61.00-150.00  109
 55  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 56  \w     76.00 110.00   1.00    1.00    --   95.80  45.00  30.00   34
 57  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 58  \w     71.00 100.00   1.00    1.00    --   95.80  61.00 120.00   29
 59  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   3.52   26
 60  \w    109.00 182.00   1.00    1.00    --   95.80  82.00 -30.00   73
 61  \w     71.00 122.00   1.00    1.00    --   95.80  61.00-180.00   51
 62  \w     71.00  97.00   1.00    1.00    --   95.80  59.00-108.23   26
 63  \w    128.00 176.00   1.00    1.00    --   95.80  59.00-108.23   48
 64  \w     43.00  68.00   1.00    1.00    --   95.80 -82.00   0.00   25
 65  \w     79.00 120.00   1.00    1.00    --   95.80 -82.00   0.00   41
 66  \w     74.00 144.00   1.00    1.00    --   95.80  50.00 172.24   70
 67  \w     63.00 178.00   1.00    1.00    --   95.80  82.00  60.00  115
 68  \w     64.00  90.00   1.00    1.00    --   95.80  82.00-150.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2321373000
_diffrn_orient_matrix_UB_12      -0.0323428000
_diffrn_orient_matrix_UB_13      -0.0130043000
_diffrn_orient_matrix_UB_21      -0.0766862000
_diffrn_orient_matrix_UB_22      -0.1103650000
_diffrn_orient_matrix_UB_23      -0.0198649000
_diffrn_orient_matrix_UB_31      -0.0233938000
_diffrn_orient_matrix_UB_32      0.0410295000
_diffrn_orient_matrix_UB_33      -0.0637944000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            41482
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         3.905
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.639
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.106
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1281 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3201
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0289
_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^)+(0.0436P)^2^+0.1799P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0733
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.713
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3120
_reflns_number_total             3201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05740j2.cif
_cod_data_source_block           exp_3313
_cod_depositor_comments          'Adding full bibliography for 1576019.cif.'
_cod_database_code               1576019
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.89
_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
2.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C12(H12A,H12B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C5(H5), C10(H10), C2(H2), C9(H9), C4(H4), C3(H3), C23(H23), C22(H22),
 C19(H19), C21(H21), C20(H20)
;
_shelx_res_checksum              86049
_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 1.577
_oxdiff_exptl_absorpt_empirical_full_min 0.660