An unexpected transition-metal free regioselective cyclization of alkynyl-tethered indoles to prepare indole-fused azepino[2,1-b]quinazolinones and spiroindole-pyrrolo[2,1-b]quinazolinones
Zou, Pei-Sen; Geng, Yi-Fan; Liu, Xiao-Qing; Su, Jun-Cheng; Pan, Cheng-Xue; Mo, Dong-Liang; Su, Gui-Fa; Green Chemistry 27 (2025) 14556–14563; doi:10.1039/D5GC04267D

data_7251019
_publ_section_title
;
 An unexpected transition-metal free regioselective cyclization of
 alkynyl-tethered indoles to prepare indole-fused
 azepino[2,1-b]quinazolinones and spiroindole-pyrrolo[2,1-b]quinazolinones
;
_journal_issue                   45
_journal_name_full               'Green Chemistry'
_journal_page_first              14556
_journal_page_last               14563
_journal_paper_doi               10.1039/D5GC04267D
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C27 H21 N3 O'
_chemical_formula_sum            'C27 H21 N3 O'
_chemical_formula_weight         403.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-04-28 deposited with the CCDC.	2025-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.4020(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.3090(3)
_cell_length_b                   12.04310(10)
_cell_length_c                   20.6182(3)
_cell_measurement_reflns_used    9672
_cell_measurement_temperature    294.7(3)
_cell_measurement_theta_max      77.0570
_cell_measurement_theta_min      4.4510
_cell_volume                     4143.59(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.7(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.956
_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    119.00 155.00   0.50    1.60    --  107.75  98.00-113.00   72
  2  \w    122.00 178.00   0.50    1.60    --  107.75  37.00  60.00  112
  3  \w    118.00 175.00   0.50    1.60    --  107.75  19.00 150.00  114
  4  \w     44.00  70.00   0.50    1.60    --  107.75 -77.00 150.00   52
  5  \w     38.00  95.00   0.50    1.60    --  107.75 -77.00 -60.00  114
  6  \w     69.00 105.00   0.50    1.60    --  107.75 -77.00-150.00   72
  7  \w     40.00  67.00   0.50    1.60    --  107.75 -77.00-150.00   54
  8  \w     35.00  60.00   0.50    1.60    --  107.75 -57.00 -90.00   50
  9  \w     38.00  88.00   0.50    1.60    --  107.75 -77.00 -30.00  100
 10  \w     37.00  63.00   0.50    1.60    --  107.75 -57.00   0.00   52
 11  \w     81.00 106.00   0.50    1.60    --  107.75 -77.00 150.00   50
 12  \w     38.00  65.00   0.50    1.60    --  107.75 -57.00 150.00   54
 13  \w     40.00  66.00   0.50    1.60    --  107.75 -57.00 -30.00   52
 14  \w     35.00  60.00   0.50    1.60    --  107.75 -57.00-150.00   50
 15  \w     36.00  94.00   0.50    1.60    --  107.75 -99.00-180.00  116
 16  \w     48.00 106.00   0.50    1.60    --  107.75 -98.00 138.00  116
 17  \w     -1.00  44.00   0.50    0.37    --   47.70 -98.00 138.00   90
 18  \w    -17.00  26.00   0.50    0.37    --  -47.70  19.00   0.00   86
 19  \w    -75.00 -13.00   0.50    1.60    --  -86.25  98.00-113.00  124
 20  \w    -40.00 -13.00   0.50    1.60    --  -86.25  37.00-180.00   54
 21  \w    -79.00  25.00   0.50    0.37    --  -47.70  98.00-113.00  208
 22  \w    -42.00 -13.00   0.50    1.60    --  -86.25  37.00  90.00   58
 23  \w   -147.00-122.00   0.50    1.60    --  -86.25 -98.00 138.00   50
 24  \w   -156.00 -86.00   0.50    1.60    --  -86.25 -99.00  60.00  140
 25  \w   -100.00 -73.00   0.50    0.37    --  -47.70-125.00 -60.00   54
 26  \w   -118.00 -75.00   0.50    0.37    --  -47.70-125.00-150.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0249643000
_diffrn_orient_matrix_UB_12      0.1177858000
_diffrn_orient_matrix_UB_13      -0.0153939000
_diffrn_orient_matrix_UB_21      -0.0874129000
_diffrn_orient_matrix_UB_22      0.0257522000
_diffrn_orient_matrix_UB_23      -0.0381564000
_diffrn_orient_matrix_UB_31      -0.0160175000
_diffrn_orient_matrix_UB_32      0.0426599000
_diffrn_orient_matrix_UB_33      0.0657021000
_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  0.0339
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            14823
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.330
_diffrn_reflns_theta_min         4.449
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59139
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             1696
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.430
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4212
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0554
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0573P)^2^+5.0610P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1421
_refine_ls_wR_factor_ref         0.1464
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3574
_reflns_number_total             4212
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc04267d2.cif
_cod_data_source_block           20221019-sgf-zps-3-78_auto
_cod_depositor_comments
'Adding full bibliography for 7251019--7251020.cif.'
_cod_database_code               7251019
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.833
_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. Uiso/Uaniso restraints and constraints
Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C8(H8A,H8B)
3.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C25(H25), C4(H4), C24(H24), C22(H22), C1(H1), C23(H23), C3(H3),
 C15(H15), C2(H2), C16(H16), C17(H17), C19(H19), C18(H18)
3.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              75438
_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 1.809
_oxdiff_exptl_absorpt_empirical_full_min 0.577