Visible-light-promoted synthesis of imidazo[1,5-<i>a</i>]indole-3-ones <i>via</i> cascade carbene N-H insertion and oxidative cyclization.
Tang, Shou-Yang; Sang, Qian-Qian; Chen, Ze-Le; Cai, Bao-Gui; Xuan, Jun; Chemical communications (Cambridge, England) 61 (2025) 17870–17873; doi:10.1039/d5cc05725f

data_7135080
_publ_section_title
;
 Visible-light-promoted synthesis of imidazo[1,5-<i>a</i>]indole-3-ones
 <i>via</i> cascade carbene N-H insertion and oxidative cyclization.
;
_journal_issue                   91
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              17870
_journal_page_last               17873
_journal_paper_doi               10.1039/d5cc05725f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C28 H24 N2 O6'
_chemical_formula_sum            'C28 H24 N2 O6'
_chemical_formula_weight         484.49
_chemical_name_systematic        1
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-25 deposited with the CCDC.	2025-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                108.063(3)
_cell_angle_beta                 102.688(3)
_cell_angle_gamma                90.502(3)
_cell_formula_units_Z            2
_cell_length_a                   9.9897(4)
_cell_length_b                   11.2443(4)
_cell_length_c                   12.1440(4)
_cell_measurement_reflns_used    5680
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.6920
_cell_measurement_theta_min      3.9040
_cell_volume                     1260.85(8)
_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 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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.968
_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     -8.00  64.00   0.50    0.50    --   40.40 -82.00-150.00  144
  2  \w    -43.00 -12.00   0.50    0.50    --   40.40 -82.00  30.00   62
  3  \w     14.00  57.00   0.50    0.50    --   40.40  82.00 -60.00   86
  4  \w     16.00  84.00   0.50    0.50    --   40.40  65.00  60.00  136
  5  \w    -47.00 -21.00   0.50    0.50    --   40.40 -65.00 -60.00   52
  6  \w     80.00 106.00   0.50    0.50    --   40.40  77.00 120.00   52
  7  \w     12.00  61.00   0.50    0.50    --   40.40 -82.00  60.00   98
  8  \w     90.00 130.00   0.50    0.50    --   40.40  82.00 -60.00   80
  9  \w     23.00  68.00   0.50    0.50    --   40.40 -82.00 -60.00   90
 10  \w    -49.00 -14.00   0.50    0.50    --   40.40 -82.00 -60.00   70
 11  \w     67.00 129.00   0.50    0.50    --   40.40  65.00 -90.00  124
 12  \w     -1.00  46.00   0.50    0.50    --   40.40 -65.00 -60.00   94
 13  \w     10.00  62.00   0.50    0.50    --   40.40 -82.00-180.00  104
 14  \w    -46.00 -21.00   0.50    0.50    --   40.40 -82.00-180.00   50
 15  \w     27.00  76.00   0.50    0.50    --   40.40  77.00 120.00   98
 16  \w     16.00 130.00   0.50    0.50    --   40.40  65.00-150.00  228
 17  \w    -38.00 -13.00   0.50    0.50    --   40.40 -82.00  60.00   50
 18  \w     40.00  66.00   0.50    0.50    --   40.40 -82.00  30.00   52
 19  \w     32.00  62.00   0.50    0.50    --   40.40  65.00 -90.00   60
 20  \w     73.00 168.00   0.50    0.50    --   94.40  33.00 120.00  190
 21  \w     69.00 144.00   0.50    0.50    --   94.40  59.00-180.00  150
 22  \w     12.00 104.00   0.50    0.50    --   94.40 -82.00-150.00  184
 23  \w     13.00 118.00   0.50    0.50    --   94.40 -82.00   0.00  210
 24  \w      5.00 114.00   0.50    0.50    --   94.40 -82.00 150.00  218
 25  \w    109.00 134.00   0.50    0.50    --   94.40 -33.00-150.00   50
 26  \w     39.00  65.00   0.50    0.50    --   94.40 -82.00  30.00   52
 27  \w     97.00 181.00   0.50    0.50    --   94.40  68.00  60.00  168
 28  \w     54.00 102.00   0.50    0.50    --   94.40 -82.00 -60.00   96
 29  \w      8.00  91.00   0.50    0.50    --   94.40 -82.00 120.00  166
 30  \w      6.00  59.00   0.50    0.50    --   94.40 -82.00 -30.00  106
 31  \w    106.00 132.00   0.50    0.50    --   94.40  33.00 -60.00   52
 32  \w     39.00  96.00   0.50    0.50    --   94.40 -82.00-180.00  114
 33  \w      5.00  67.00   0.50    0.50    --   94.40 -82.00  60.00  124
 34  \w     28.00  79.00   0.50    0.50    --   94.40 -82.00-120.00  102
 35  \w      5.00  98.00   0.50    0.50    --   94.40 -82.00 -90.00  186
 36  \w     79.00 183.00   0.50    0.50    --   94.40  50.00 150.00  208
 37  \w     71.00 101.00   0.50    0.50    --   94.40 -82.00  60.00   60
 38  \w    158.00 183.00   0.50    0.50    --   94.40  68.00-150.00   50
 39  \w     81.00 153.00   0.50    0.50    --   94.40  68.00-150.00  144
 40  \w    110.00 137.00   0.50    0.50    --   94.40  82.00   0.00   54
 41  \w      5.00  39.00   0.50    0.50    --   94.40 -33.00-150.00   68
 42  \w     51.00  77.00   0.50    0.50    --   94.40 -82.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1141954000
_diffrn_orient_matrix_UB_12      0.0312513000
_diffrn_orient_matrix_UB_13      -0.0924050000
_diffrn_orient_matrix_UB_21      -0.0066299000
_diffrn_orient_matrix_UB_22      -0.1349129000
_diffrn_orient_matrix_UB_23      -0.0853755000
_diffrn_orient_matrix_UB_31      -0.1098910000
_diffrn_orient_matrix_UB_32      -0.0416363000
_diffrn_orient_matrix_UB_33      0.0548399000
_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  0.0619
_diffrn_reflns_av_unetI/netI     0.0616
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10250
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        66.589
_diffrn_reflns_theta_max         66.589
_diffrn_reflns_theta_min         3.938
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.746
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26988
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         4308
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.134
_refine_ls_R_factor_all          0.0869
_refine_ls_R_factor_gt           0.0771
_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^)+(0.1546P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2214
_refine_ls_wR_factor_ref         0.2364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3305
_reflns_number_total             4308
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05725f2.cif
_cod_data_source_block           exp_3215_auto
_cod_depositor_comments          'Adding full bibliography for 7135080.cif.'
_cod_database_code               7135080
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.950
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O33 \\sim C32 \\sim O35: within 2.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 2.7A
3. Others
 Fixed Sof: C34(0.75) H34A(0.75) H34B(0.75) H34C(0.75) C2(0.25) H2A(0.25)
 H2B(0.25) H2C(0.25)
4.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C18(H18), C22(H22), C26(H26), C17(H17), C10(H10), C15(H15), C7(H7),
 C9(H9), C25(H25), C23(H23), C8(H8)
4.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C34(H34A,H34B,
 H34C), C2(H2A,H2B,H2C)
;
_shelx_res_checksum              16573
_shelx_hkl_checksum              73430
_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 8.353
_oxdiff_exptl_absorpt_empirical_full_min 0.251