Rh(III)-Catalyzed Cascade C-H Activation/Amination Enables the Synthesis of 1,2-Disubstituted Benzimidazoles from Amidines and Arynes
Xu, Fen; Zhang, Shi-Yu; Huo, Jia-Qi; Zeng, Fan-Wang; Zhou, Fu-Kang; Barboni, Luciano; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D6OB00074F

data_7161093
_publ_section_title
;
 Rh(III)-catalyzed cascade C-H activation/amination enables the synthesis
 of 1,2-disubstituted benzimidazoles from amidines and arynes.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3218
_journal_page_last               3222
_journal_paper_doi               10.1039/d6ob00074f
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C20 H17 N2 O, C20 H17 N3'
_chemical_formula_sum            'C40 H34 N5 O'
_chemical_formula_weight         600.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2026-01-14
_audit_creation_method
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Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
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_audit_update_record
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2026-01-14 deposited with the CCDC.	2026-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.504(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.2779(13)
_cell_length_b                   11.148(2)
_cell_length_c                   22.875(5)
_cell_measurement_reflns_used    7205
_cell_measurement_temperature    131.9(2)
_cell_measurement_theta_max      25.1000
_cell_measurement_theta_min      3.2250
_cell_volume                     1587.2(6)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      131.9(2)
_diffrn_detector_area_resol_mean 16.2116
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
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  1 omega  -12.00   87.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372   77.0000  120.0000 99

  2 omega  -10.00   16.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372  -57.0000 -120.0000 26

  3 omega  -20.00   60.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372  -99.0000 -120.0000 80

  4 omega  -46.00    7.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372  -77.0000   90.0000 53

  5 omega  -12.00   21.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372   77.0000   30.0000 33

  6 omega  -26.00   44.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372  -37.0000  -30.0000 70

  7 omega    2.00   43.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372   57.0000 -120.0000 41

  8 omega   11.00   37.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0372   57.0000  -90.0000 26

  9 omega  -64.00  -35.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8185 -178.0000 -180.0000 29

 10 omega  -88.00  -18.00   1.0000   17.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8185  -77.0000  -30.0000 70
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0412144000
_diffrn_orient_matrix_UB_12      -0.0304618000
_diffrn_orient_matrix_UB_13      -0.0075915000
_diffrn_orient_matrix_UB_21      -0.0215789000
_diffrn_orient_matrix_UB_22      0.0113226000
_diffrn_orient_matrix_UB_23      0.0245186000
_diffrn_orient_matrix_UB_31      -0.0193623000
_diffrn_orient_matrix_UB_32      0.0210923000
_diffrn_orient_matrix_UB_33      -0.0202106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0669
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            9373
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.827
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62712
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             634
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.348
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.094
_refine_ls_extinction_coef       0.059(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         5439
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.1706
_refine_ls_R_factor_gt           0.1327
_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^)+(0.1266P)^2^+8.3833P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3759
_refine_ls_wR_factor_ref         0.4017
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3503
_reflns_number_total             5439
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00074f2.cif
_cod_data_source_block           260111lu_yq_zz_0773097_zcs_0m
_cod_depositor_comments
'Adding full bibliography for 7161092--7161093.cif.'
_cod_database_code               7161093
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C Zn'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 O1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C18(H18), C19(H19), N004(H004), C00K(H00K),
 C00M(H00M), C00P(H00P), C00Q(H00Q), C00S(H00S), C00T(H00T), C00Y(H00Y),
 C011(H011), C012(H012), C013(H013), C015(H015), C016(H016), C018(H018)
2.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C019(H01A,H01B,H01C)
;
_shelx_res_checksum              76886
_olex2_submission_special_instructions 'No special instructions were received'