Iridium-Catalyzed Intramolecular Asymmetric Allylic Amination of Anthranilic Acid Derivatives: Enantioselective Construction of Chiral Benzodiazepinones
Wu, Yunru; Pan, Bendu; Jiang, Long; Cao, Rihui; Qiu, Liqin; Chemical Communications  (2026) –; doi:10.1039/D6CC00993J

data_7135660
_publ_section_title
;
 Iridium-catalyzed intramolecular asymmetric allylic amination of
 anthranilic acid derivatives: enantioselective construction of chiral
 benzodiazepinones.
;
_journal_issue                   30
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7857
_journal_page_last               7860
_journal_paper_doi               10.1039/d6cc00993j
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H26 N2 O'
_chemical_formula_sum            'C26 H26 N2 O'
_chemical_formula_weight         382.49
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-10-16 deposited with the CCDC.	2026-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.42816(5)
_cell_length_b                   11.09278(9)
_cell_length_c                   22.92566(15)
_cell_measurement_reflns_used    59712
_cell_measurement_temperature    293.5(5)
_cell_measurement_theta_max      75.9210
_cell_measurement_theta_min      3.8563
_cell_volume                     2143.36(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.5(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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    -66.00  33.00   1.00    1.00    --  -41.14  38.00  30.00   99
  2  \w      6.00  81.00   1.00    1.00    --   41.14 -99.00 -90.00   75
  3  \w    -31.00  69.00   1.00    1.00    --   41.14 -57.00-180.00  100
  4  \w     27.00  95.00   1.00    1.00    --   41.14-125.00   0.00   68
  5  \w     84.00 178.00   1.00    3.00    --  112.00  30.00  90.00   94
  6  \w    104.00 178.00   1.00    3.00    --  112.00 111.00 -30.00   74
  7  \w    103.00 178.00   1.00    3.00    --  112.00  77.00   0.00   75
  8  \w     36.00 145.00   1.00    3.00    --  112.00 -77.00  60.00  109
  9  \w     39.00 109.00   1.00    3.00    --  112.00-111.00 -30.00   70
 10  \w    103.00 178.00   1.00    3.00    --  112.00  77.00 150.00   75
 11  \w     39.00 109.00   1.00    3.00    --  112.00-114.00  73.00   70
 12  \w     58.00 151.00   1.00    3.00    --  112.00-178.00   0.00   93
 13  \w     40.00 141.00   1.00    3.00    --  112.00 -61.00-120.00  101
 14  \w   -114.00 -13.00   1.00    1.00    --  -41.14 -57.00 150.00  101
 15  \w   -114.00 -13.00   1.00    1.00    --  -41.14 -57.00 -90.00  101
 16  \w   -114.00 -13.00   1.00    1.00    --  -41.14 -57.00  30.00  101
 17  \w     84.00 144.00   1.00    3.00    --  112.00  30.00   0.00   60
 18  \w     59.00 178.00   1.00    3.00    --  112.00  15.00-150.00  119
 19  \w     59.00 178.00   1.00    3.00    --  112.00  15.00 -60.00  119
 20  \w   -114.00 -13.00   1.00    1.00    --  -41.52 -57.00-150.00  101
 21  \w   -114.00 -13.00   1.00    1.00    --  -41.52 -57.00  90.00  101
 22  \w   -114.00 -19.00   1.00    1.00    --  -41.52 -57.00 -30.00   95
 23  \w    -87.00  -6.00   1.00    1.00    --  -41.52 125.00  60.00   81
 24  \w   -122.00  -1.00   1.00    1.00    --  -41.52 -19.00  30.00  121
 25  \w   -116.00 -17.00   1.00    1.00    --  -41.52 -38.00-150.00   99
 26  \w   -114.00 -13.00   1.00    1.00    --  -41.52 -57.00   0.00  101
 27  \w   -116.00 -17.00   1.00    1.00    --  -41.52 -38.00-120.00   99
 28  \w   -116.00 -17.00   1.00    1.00    --  -41.52 -38.00  30.00   99
 29  \w   -122.00  -1.00   1.00    1.00    --  -41.52 -19.00  90.00  121
 30  \w   -116.00 -17.00   1.00    1.00    --  -41.52 -38.00 -90.00   99
 31  \w      6.00  81.00   1.00    1.00    --   41.52 -99.00  60.00   75
 32  \w   -116.00 -17.00   1.00    2.00    --  -41.52 -38.00 120.00   99
 33  \w   -114.00 -13.00   1.00    2.00    --  -41.52 -57.00 120.00  101
 34  \w   -116.00 -17.00   1.00    2.00    --  -41.52 -38.00 -30.00   99
 35  \w     13.00 114.00   1.00    2.00    --   41.52  57.00 -90.00  101
 36  \w     13.00 114.00   1.00    2.00    --   41.52  57.00-120.00  101
 37  \w     13.00 114.00   1.00    2.00    --   41.52  57.00  30.00  101
 38  \w    -47.00   5.00   1.00    2.00    --   41.52   0.00-180.00   52
 39  \w     13.00 114.00   1.00    2.00    --   41.52  57.00-180.00  101
 40  \w     27.00  96.00   1.00    2.00    --   41.52-125.00 150.00   69
 41  \w   -130.00  45.00   1.00    4.00    --  -41.52   0.00-150.00  175
 42  \w   -130.00  47.00   1.00    5.00    --  -41.52   0.00-180.00  177
 43  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00-120.00  177
 44  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 -60.00  177
 45  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 -30.00  177
 46  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00   0.00  177
 47  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00  60.00  177
 48  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00  30.00  177
 49  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00  90.00  177
 50  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 120.00  177
 51  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 150.00  177
 52  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 -90.00  177
 53  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00-150.00  177
 54  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00-180.00  177
 55  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00-150.00  177
 56  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00-120.00  177
 57  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 -90.00  177
 58  \w    -47.00 130.00   1.00    5.00    --   41.52   0.00 -60.00  177
 59  \w    -47.00  66.00   1.00    5.00    --   41.52   0.00 -30.00  113
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0876466000
_diffrn_orient_matrix_UB_12      0.0756726000
_diffrn_orient_matrix_UB_13      -0.0462368000
_diffrn_orient_matrix_UB_21      0.1573328000
_diffrn_orient_matrix_UB_22      0.0191980000
_diffrn_orient_matrix_UB_23      -0.0329448000
_diffrn_orient_matrix_UB_31      -0.0314143000
_diffrn_orient_matrix_UB_32      -0.1148341000
_diffrn_orient_matrix_UB_33      -0.0359478000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0162
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            70844
_diffrn_reflns_theta_full        76.21
_diffrn_reflns_theta_max         76.21
_diffrn_reflns_theta_min         3.86
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.561
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62352
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.185
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.045
_exptl_crystal_size_mid          0.032
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.120
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(3)
_refine_ls_extinction_coef       0.0092(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         4394
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0370
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0653P)^2^+0.1515P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1028
_reflns_number_gt                4250
_reflns_number_total             4394
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d6cc00993j2.cif
_cod_data_source_block           q
_cod_depositor_comments          'Adding full bibliography for 7135660.cif.'
_cod_database_code               7135660
_chemical_oxdiff_formula         C26H26N2O
_chemical_oxdiff_usercomment     QLQ-
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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 Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C13(H13A,H13B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
2.d X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.540
_oxdiff_exptl_absorpt_empirical_full_min 0.695