Synthesis of seven-membered azepino[3,2,1-hi]indoles via rhodium-catalyzed regioselectively C-H activation/DBU-catalyzed intramolecualr amidation of 7-phenylindoles in one pot.
Yuan, Yumeng; Pan, Guoshuai; Zhang, Xiaofeng; Li, Buhong; Xiang, Shengchang; Huang, Qiufeng; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02289

data_4034694
_publ_section_title
;
 Synthesis of seven-membered azepino[3,2,1-hi]indoles via
 rhodium-catalyzed regioselectively C-H activation/DBU-catalyzed
 intramolecualr amidation of 7-phenylindoles in one pot.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02289
_journal_year                    2019
_chemical_formula_moiety         'C20 H15 N O4'
_chemical_formula_sum            'C20 H15 N O4'
_chemical_formula_weight         333.33
_chemical_name_systematic        Y
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.306(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.47677(15)
_cell_length_b                   12.5741(4)
_cell_length_c                   23.3420(6)
_cell_measurement_reflns_used    2951
_cell_measurement_temperature    294.54(13)
_cell_measurement_theta_max      72.6830
_cell_measurement_theta_min      3.7630
_cell_volume                     1602.92(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.54(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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    -65.00  34.00   1.00    1.89    --  -40.45  38.00  30.00   99
  2  \w    -69.00  33.00   1.00    1.89    --  -40.45  57.00 120.00  102
  3  \w    -65.00  34.00   1.00    1.89    --  -40.45  38.00-150.00   99
  4  \w     71.00 178.00   1.00    7.55    --  103.24  77.00  30.00  107
  5  \w     30.00 129.00   1.00    7.55    --  103.24 -45.00 150.00   99
  6  \w     94.00 176.00   1.00    7.55    --  103.24 125.00-150.00   82
  7  \w     94.00 176.00   1.00    7.55    --  103.24 125.00 120.00   82
  8  \w     21.00 109.00   1.00    7.55    --  103.24 -94.00 -30.00   88
  9  \w    101.00 178.00   1.00    7.55    --  103.24  91.00  60.00   77
 10  \w     21.00  71.00   1.00    7.55    --  103.24 -94.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1027112000
_diffrn_orient_matrix_UB_12      -0.1119702000
_diffrn_orient_matrix_UB_13      -0.0137288000
_diffrn_orient_matrix_UB_21      -0.0885098000
_diffrn_orient_matrix_UB_22      -0.0076700000
_diffrn_orient_matrix_UB_23      0.0610005000
_diffrn_orient_matrix_UB_31      -0.2472350000
_diffrn_orient_matrix_UB_32      0.0491817000
_diffrn_orient_matrix_UB_33      -0.0217458000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            8554
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.686
_diffrn_reflns_theta_min         3.996
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.798
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76807
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.381
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.151
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3114
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0608P)^2^+0.2685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2479
_reflns_number_total             3114
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02289_si_010.cif
_cod_data_source_block           y-181
_cod_original_cell_volume        1602.93(8)
_cod_database_code               4034694
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C15(H15), C18(H18), C19(H19), C21(H21), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              22880
_shelx_hkl_checksum              54816
_olex2_date_sample_data_collection 2019-07-15
_olex2_submission_original_sample_id 181
_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 1.513
_oxdiff_exptl_absorpt_empirical_full_min 0.597