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_4034695
_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         'C18 H13 N O3'
_chemical_formula_sum            'C18 H13 N O3'
_chemical_formula_weight         291.29
_chemical_name_systematic        Y2
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.940(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.3481(6)
_cell_length_b                   8.6768(4)
_cell_length_c                   21.2841(8)
_cell_measurement_reflns_used    5376
_cell_measurement_temperature    294.31(15)
_cell_measurement_theta_max      72.3170
_cell_measurement_theta_min      3.6240
_cell_volume                     2827.8(2)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.31(15)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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   -120.00   1.00   1.00    2.50    --  -40.45 -19.00   0.00  121
  2  \w    -92.00  -2.00   1.00    2.50    --  -40.45 125.00-180.00   90
  3  \w    -65.00  34.00   1.00    2.50    --  -40.45  38.00-180.00   99
  4  \w      1.00  81.00   1.00    2.50    --   40.45 -99.00 -60.00   80
  5  \w     31.00 132.00   1.00    7.50    --  103.24 -61.00   0.00  101
  6  \w     77.00 176.00   1.00    7.50    --  103.24  45.00 -90.00   99
  7  \w     21.00 109.00   1.00    7.50    --  103.24 -94.00-120.00   88
  8  \w     30.00 117.00   1.00    7.50    --  103.24-125.00  90.00   87
  9  \w     30.00 117.00   1.00    7.50    --  103.24-125.00 -30.00   87
 10  \w     58.00 116.00   1.00    7.50    --  103.24-125.00-180.00   58
 11  \w     95.00 176.00   1.00    7.50    --  103.24  45.00 150.00   81
;
_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      -0.0331069000
_diffrn_orient_matrix_UB_12      0.1653265000
_diffrn_orient_matrix_UB_13      0.0099523000
_diffrn_orient_matrix_UB_21      0.0900216000
_diffrn_orient_matrix_UB_22      0.0642929000
_diffrn_orient_matrix_UB_23      -0.0145163000
_diffrn_orient_matrix_UB_31      -0.0304024000
_diffrn_orient_matrix_UB_32      0.0101379000
_diffrn_orient_matrix_UB_33      -0.0703271000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0239
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            16224
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.546
_diffrn_reflns_theta_min         3.441
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.767
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90571
_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    1.368
_exptl_crystal_description       plate
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.131
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         5522
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0617P)^2^+0.3752P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1186
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4403
_reflns_number_total             5522
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02289_si_003.cif
_cod_data_source_block           y2-032
_cod_depositor_comments
;

2020-08-05
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C18 H13 N O3)'
_cod_original_formula_sum        'C36 H26 N2 O6'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     582.59
_cod_database_code               4034695
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.94
_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:
 C00J(H00J), C00K(H00K)
2.b Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00N(H00N), C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010),
 C011(H011), C012(H012), C013(H013), C014(H014), C015(H015), C016(H016)
2.c Idealised Me refined as rotating group:
 C017(H01D,H01E,H01F), C018(H01A,H01B,H01C)
;
_shelx_res_checksum              9261
_shelx_hkl_checksum              79331
_olex2_submission_original_sample_id 032
_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 1.180
_oxdiff_exptl_absorpt_empirical_full_min 0.808