New axially chiral biaryl quinoline ligands specifically partnered with AgOTf enabled an enantioselective aza-Friedel-Crafts reaction.
Gao, Su-Fan; Fu, Xiao; Zhang, Qian-Mao; Tang, Ren-Zhi; Wan, Wen-Juan; Wang, Li-Xin; Organic & biomolecular chemistry 23 (2025) 4100–4105; doi:10.1039/d5ob00231a

data_7160435
_publ_section_title
;
 New axially chiral biaryl quinoline ligands specifically partnered with
 AgOTf enabled an enantioselective aza-Friedel-Crafts reaction.
;
_journal_issue                   17
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4100
_journal_page_last               4105
_journal_paper_doi               10.1039/d5ob00231a
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H27 N3 O3'
_chemical_formula_sum            'C28 H27 N3 O3'
_chemical_formula_weight         453.52
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-11-08 deposited with the CCDC.	2025-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.54932(14)
_cell_length_b                   10.64007(18)
_cell_length_c                   21.4433(3)
_cell_measurement_reflns_used    13212
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.9520
_cell_measurement_theta_min      4.1190
_cell_volume                     2406.91(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     18.00  43.00   1.00    1.00    --    0.00  37.00 -30.00   25
  2  \w     11.00  36.00   1.00    1.60    --  -33.50  77.00 120.00   25
  3  \w    -53.00 -20.00   1.00    1.60    --  -33.50  37.00  90.00   33
  4  \w    -60.00 -15.00   1.00    1.60    --  -33.50  77.00 120.00   45
  5  \w    -91.00 -23.00   1.00    1.60    --  -33.50 -57.00-150.00   68
  6  \w      9.00  35.00   1.00    1.60    --   36.47  74.00 127.70   26
  7  \w      0.00  25.00   1.00    1.60    --   36.47  91.00-178.96   25
  8  \w      8.00  33.00   1.00    1.60    --   36.47 -99.00-180.00   25
  9  \w     19.00 103.00   1.00    1.60    --   36.47  57.00   0.00   84
 10  \w     12.00  38.00   1.00    1.60    --   36.47  76.00 166.42   26
 11  \w      4.00  37.00   1.00    1.60    --   36.47  85.00 -73.14   33
 12  \w     71.00  97.00   1.00    1.60    --   36.47  37.00  60.00   26
 13  \w      3.00  29.00   1.00    1.60    --   36.47  91.00  28.14   26
 14  \w     45.00  72.00   1.00    1.60    --   36.47 -99.00 -90.00   27
 15  \w     21.00  53.00   1.00    1.60    --   36.47  57.00  60.00   32
 16  \w      3.00  34.00   1.00    1.60    --   36.47  89.00-152.43   31
 17  \w     61.00 101.00   1.00    1.60    --   36.47 178.00-120.00   40
 18  \w      0.00  25.00   1.00    1.60    --   36.47  91.00 109.22   25
 19  \w     38.00  77.00   1.00    1.60    --   36.47  57.00 -60.00   39
 20  \w     61.00 110.00   1.00    1.60    --   36.47 178.00  60.00   49
 21  \w     20.00  47.00   1.00    1.60    --   36.47  37.00  60.00   27
 22  \w     15.00  40.00   1.00    1.60    --   36.47  37.00-120.00   25
 23  \w     14.00  40.00   1.00    1.60    --   36.47 -99.00 -90.00   26
 24  \w     64.00  90.00   1.00    1.60    --   36.47  57.00 150.00   26
 25  \w     64.00 107.00   1.00    1.60    --   36.47 178.00 -30.00   43
 26  \w      7.00  36.00   1.00    1.60    --   36.47  80.00-107.20   29
 27  \w     88.00 121.00   1.00    9.50    --  108.00  61.00  30.00   33
 28  \w     44.00  71.00   1.00    9.50    --  108.00 -94.00 120.00   27
 29  \w     41.00  72.00   1.00    9.50    --  108.00 -94.00  30.00   31
 30  \w    139.00 176.00   1.00    9.50    --  108.00  61.00  30.00   37
 31  \w    149.00 174.00   1.00    9.50    --  108.00  61.00 150.00   25
 32  \w     82.00 158.00   1.00    9.50    --  108.00  30.00 120.00   76
 33  \w    143.00 178.00   1.00    9.50    --  108.00  45.00  60.00   35
 34  \w     88.00 115.00   1.00    9.50    --  108.00  61.00 150.00   27
 35  \w     84.00 111.00   1.00    9.50    --  108.00  30.00 150.00   27
 36  \w     88.00 114.00   1.00    9.50    --  108.00  61.00  60.00   26
 37  \w    117.00 170.00   1.00    9.50    --  108.00  30.00  90.00   53
 38  \w     88.00 114.00   1.00    9.50    --  108.00  45.00 120.00   26
 39  \w     89.00 137.00   1.00    9.50    --  108.00  45.00  60.00   48
 40  \w    138.00 177.00   1.00    9.50    --  108.00  -3.00-151.89   39
 41  \w    106.00 132.00   1.00    9.50    --  108.00 -77.00-180.00   26
 42  \w     84.00 110.00   1.00    9.50    --  108.00  30.00  60.00   26
 43  \w     74.00 100.00   1.00    9.50    --  108.00-111.00 120.00   26
 44  \w     40.00  75.00   1.00    9.50    --  108.00 -77.00-180.00   35
 45  \w    113.00 139.00   1.00    9.50    --  108.00  30.00  60.00   26
 46  \w     83.00 111.00   1.00    9.50    --  108.00  30.00  90.00   28
 47  \w    108.00 147.00   1.00    9.50    --  108.00 111.00   0.00   39
 48  \w     89.00 115.00   1.00    9.50    --  108.00  45.00-180.00   26
 49  \w    115.00 159.00   1.00    9.50    --  108.00  45.00 -60.00   44
 50  \w     39.00  65.00   1.00    9.50    --  108.00 -94.00-120.00   26
 51  \w     41.00  90.00   1.00    9.50    --  108.00 -94.00 150.00   49
 52  \w    153.00 178.00   1.00    9.50    --  108.00  30.00-180.00   25
 53  \w     38.00  80.00   1.00    9.50    --  108.00 -94.00 -60.00   42
 54  \w     83.00 116.00   1.00    9.50    --  108.00  30.00-180.00   33
 55  \w    142.00 173.00   1.00    9.50    --  108.00  77.00 120.00   31
 56  \w    132.00 168.00   1.00    9.50    --  108.00  45.00 150.00   36
 57  \w     41.00  85.00   1.00    9.50    --  108.00-111.00 -60.00   44
 58  \w     76.00 107.00   1.00    9.50    --  108.00 -94.00  30.00   31
 59  \w     88.00 177.00   1.00    9.50    --  108.00  45.00 -30.00   89
 60  \w     48.00  74.00   1.00    9.50    --  108.00-111.00  30.00   26
 61  \w     84.00 109.00   1.00    9.50    --  108.00-111.00  30.00   25
 62  \w    106.00 170.00   1.00    9.50    --  108.00 111.00-150.00   64
 63  \w     49.00  99.00   1.00    9.50    --  108.00 -30.00   0.00   50
 64  \w     89.00 114.00   1.00    9.50    --  108.00  61.00  90.00   25
 65  \w     88.00 114.00   1.00    9.50    --  108.00  45.00 150.00   26
 66  \w     89.00 114.00   1.00    9.50    --  108.00  30.00  30.00   25
 67  \w    100.00 126.00   1.00    9.50    --  108.00 -61.00 -60.00   26
 68  \w     65.00  91.00   1.00    9.50    --  108.00 -61.00 -60.00   26
 69  \w     88.00 113.00   1.00    9.50    --  108.00  45.00  90.00   25
 70  \w     88.00 114.00   1.00    9.50    --  108.00  61.00 120.00   26
 71  \w    125.00 173.00   1.00    9.50    --  108.00  77.00 -90.00   48
 72  \w     42.00  73.00   1.00    9.50    --  108.00 -94.00  90.00   31
 73  \w     83.00 109.00   1.00    9.50    --  108.00-111.00 -30.00   26
 74  \w    101.00 133.00   1.00    9.50    --  108.00  77.00 120.00   32
 75  \w     89.00 115.00   1.00    9.50    --  108.00  45.00  30.00   26
 76  \w     82.00 107.00   1.00    9.50    --  108.00 -94.00-180.00   25
 77  \w     61.00  87.00   1.00    9.50    --  108.00 -61.00 -90.00   26
 78  \w     47.00  73.00   1.00    9.50    --  108.00  -3.00-151.89   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1295130000
_diffrn_orient_matrix_UB_12      0.0098762000
_diffrn_orient_matrix_UB_13      -0.0328420000
_diffrn_orient_matrix_UB_21      0.0656140000
_diffrn_orient_matrix_UB_22      -0.0517844000
_diffrn_orient_matrix_UB_23      0.0587988000
_diffrn_orient_matrix_UB_31      -0.0157303000
_diffrn_orient_matrix_UB_32      -0.1348595000
_diffrn_orient_matrix_UB_33      -0.0249987000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29186
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.983
_diffrn_reflns_theta_min         4.123
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.659
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93379
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.214
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 1782 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4624
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0802P)^2^+0.2059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1209
_reflns_Friedel_coverage         0.755
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4353
_reflns_number_total             4624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00231a2.cif
_cod_data_source_block           202410332_auto
_cod_depositor_comments          'Adding full bibliography for 7160435.cif.'
_cod_database_code               7160435
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C28H31O2N2
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.896
_reflns_odcompleteness_completeness 87.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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:
 C17(H17A,H17B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C13(H13), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              70557
_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 1.180
_oxdiff_exptl_absorpt_empirical_full_min 0.926