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_7251020
_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         'C25 H17 N3 O'
_chemical_formula_sum            'C25 H17 N3 O'
_chemical_formula_weight         375.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-04-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-14 deposited with the CCDC.	2025-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.885(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4831(3)
_cell_length_b                   11.2094(4)
_cell_length_c                   15.2029(5)
_cell_measurement_reflns_used    9250
_cell_measurement_temperature    294.24(16)
_cell_measurement_theta_max      75.4840
_cell_measurement_theta_min      2.8970
_cell_volume                     1954.42(11)
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      294.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.942
_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    -67.00  31.00   0.50    0.60    --  -43.18  65.00 -76.00  196
  2  \w     19.00 117.00   0.50    0.60    --   43.18  65.00 -76.00  196
  3  \w    -30.00  46.00   0.50    0.60    --   43.18 -65.00 148.00  152
  4  \w    -55.00 -29.00   0.50    2.50    --  -90.25  65.00 -76.00   52
  5  \w   -139.00-114.00   0.50    2.50    --  -90.25 -65.00 148.00   50
  6  \w     90.00 143.00   0.50    2.50    --  109.26  65.00 -76.00  106
  7  \w    149.00 177.00   0.50    2.50    --  109.26  65.00 -76.00   56
  8  \w     37.00  63.00   0.50    2.50    --  109.26 -65.00 148.00   52
  9  \w   -112.00 -21.00   0.50    0.60    --  -43.18 -65.00 148.00  182
 10  \w    -31.00  24.00   0.50    0.60    --   43.18 -19.00-180.00  110
 11  \w     34.00  97.00   0.50    0.60    --   43.18-125.00   0.00  126
 12  \w    -51.00 -16.00   0.50    2.50    --  -90.25  45.00 150.00   70
 13  \w    -53.00 -16.00   0.50    2.50    --  -90.25 125.00-180.00   74
 14  \w    -44.00 -16.00   0.50    2.50    --  -90.25  45.00 120.00   56
 15  \w    -49.00 -21.00   0.50    2.50    --  -90.25  45.00  90.00   56
 16  \w    -49.00 -15.00   0.50    2.50    --  -90.25  45.00-120.00   68
 17  \w     76.00 102.00   0.50    2.50    --  109.26-125.00  30.00   52
 18  \w     90.00 151.00   0.50    2.50    --  109.26  45.00-150.00  122
 19  \w     37.00 105.00   0.50    2.50    --  109.26 -94.00 -90.00  136
 20  \w     36.00  63.00   0.50    2.50    --  109.26-125.00  30.00   54
 21  \w     36.00  63.00   0.50    2.50    --  109.26 -61.00 -30.00   54
 22  \w     36.00  68.00   0.50    2.50    --  109.26-125.00-120.00   64
 23  \w     36.00  62.00   0.50    2.50    --  109.26 -61.00  30.00   52
 24  \w     36.00  63.00   0.50    2.50    --  109.26 -61.00  90.00   54
 25  \w     68.00  95.00   0.50    2.50    --  109.26 -77.00 -60.00   54
 26  \w     38.00  63.00   0.50    2.50    --  109.26 -77.00 -60.00   50
 27  \w     37.00  65.00   0.50    2.50    --  109.26 -61.00  60.00   56
 28  \w     86.00 111.00   0.50    2.50    --  109.26-125.00-120.00   50
 29  \w     44.00  69.00   0.50    2.50    --  109.26 -61.00   0.00   50
 30  \w     36.00  61.00   0.50    2.50    --  109.26 -61.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12674
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.177
_diffrn_reflns_theta_min         4.714
_exptl_absorpt_coefficient_mu    0.631
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54545
_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    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.312
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.074
_refine_ls_extinction_coef       0.0036(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3857
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.1347
_refine_ls_R_factor_gt           0.1280
_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^)+(0.1145P)^2^+4.2897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3160
_refine_ls_wR_factor_ref         0.3203
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3517
_reflns_number_total             3857
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc04267d2.cif
_cod_data_source_block           20221020-sgf-zps-3-17_auto
_cod_depositor_comments
'Adding full bibliography for 7251019--7251020.cif.'
_cod_database_code               7251020
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.833
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00C(H00C), C00D(H00D), C00F(H00F), C00G(H00G), C00H(H00H),
 C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O), C00Q(H00Q),
 C00R(H00R), C00S(H00S)
1.b Idealised Me refined as rotating group:
 C00T(H00B,H00E,H00I)
;
_shelx_res_checksum              41142
_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
;