Directing group switch in copper-catalyzed electrophilic C–H amination/migratory annulation cascade: divergent access to benzimidazolone/benzimidazole
Begam, Hasina Mamataj; Nandi, Shantanu; Jana, Ranjan; Chemical Science  (2022) –; doi:10.1039/D2SC01420C

data_1566801
_publ_section_title
;
 Directing group switch in copper-catalyzed electrophilic C--H
 amination/migratory annulation cascade: divergent access to
 benzimidazolone/benzimidazole
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01420C
_journal_year                    2022
_chemical_formula_moiety         'C21 H19 N3'
_chemical_formula_sum            'C21 H19 N3'
_chemical_formula_weight         313.41
_chemical_melting_point          418
_chemical_name_common
3-cyclopentyl-2-(pyridin-2-yl)-3H-naphtho[1,2-d]imidazole
_chemical_name_systematic        HM_788
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-08-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-08-25 deposited with the CCDC.	2022-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.217(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2933(10)
_cell_length_b                   5.6759(9)
_cell_length_c                   18.003(3)
_cell_measurement_reflns_used    8481
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.802
_cell_measurement_theta_min      2.928
_cell_volume                     1542.5(4)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.9741
_diffrn_measured_fraction_theta_max 0.9741
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0804
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22846
_diffrn_reflns_theta_full        71.8530
_diffrn_reflns_theta_max         71.85
_diffrn_reflns_theta_min         2.93
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5593
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1643 before and 0.0888 after correction. The Ratio of minimum to maximum transmission is 0.7422. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.3495
_exptl_crystal_description       block
_exptl_crystal_F_000             665.8690
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane, petroleum ether'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.2232
_refine_diff_density_min         -0.3427
_refine_diff_density_rms         0.0628
_refine_ls_d_res_high            0.8112
_refine_ls_d_res_low             15.0958
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0483
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    34
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2934
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0483
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0531
_refine_ls_shift/su_max          0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0759P)^2^+0.7325P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1361
_refine_ls_wR_factor_ref         0.1400
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              18
_reflns_limit_h_min              -18
_reflns_limit_k_max              6
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                2676
_reflns_number_total             2934
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d2sc01420c2.cif
_cod_data_source_block           HM_788_1_0m_a
_cod_database_code               1566801
_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:
 C00L(H00o)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00a,H00d), C00F(H00f,H00g), C00G(H00h,H00i), C00K(H00m,H00n)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00B(H00B), C00C(H00C), C00E(H00E), C00H(H00j), C00I(H00k),
 C00J(H00l), C00M(H00p), C00N(H00q), C00O(H00r)
;
_olex2_submission_special_instructions 'No special instructions were received'