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_4034687
_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         'C19 H15 N O3'
_chemical_formula_sum            'C19 H15 N O3'
_chemical_formula_weight         305.32
_chemical_name_systematic        y2
_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             2019-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                79.529(5)
_cell_angle_beta                 87.131(5)
_cell_angle_gamma                85.915(5)
_cell_formula_units_Z            2
_cell_length_a                   8.1949(5)
_cell_length_b                   8.5852(5)
_cell_length_c                   10.9177(7)
_cell_measurement_reflns_used    3387
_cell_measurement_temperature    296.2(4)
_cell_measurement_theta_max      72.7750
_cell_measurement_theta_min      4.0910
_cell_volume                     752.86(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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.2(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.974
_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    -92.00  -2.00   1.00    2.00    --  -40.45 125.00 -90.00   90
  2  \w   -117.00  -8.00   1.00    2.00    --  -40.45 -77.00-150.00  109
  3  \w     23.00  96.00   1.00    2.00    --   40.45-125.00-180.00   73
  4  \w     12.00 113.00   1.00    2.00    --   40.45  57.00  30.00  101
  5  \w     16.00 115.00   1.00    2.00    --   40.45  38.00 150.00   99
  6  \w     30.00 117.00   1.00    6.00    --  103.24-125.00   0.00   87
  7  \w     74.00 176.00   1.00    6.00    --  103.24  61.00 -60.00  102
  8  \w     30.00 129.00   1.00    6.00    --  103.24 -45.00 150.00   99
  9  \w     30.00 117.00   1.00    6.00    --  103.24-125.00 120.00   87
 10  \w     21.00 109.00   1.00    6.00    --  103.24 -94.00-180.00   88
 11  \w     77.00 176.00   1.00    6.00    --  103.24  45.00   0.00   99
 12  \w     30.00 129.00   1.00    6.00    --  103.24 -45.00 -60.00   99
 13  \w     27.00 136.00   1.00    6.00    --  103.24 -77.00-120.00  109
 14  \w     75.00 178.00   1.00    6.00    --  103.24  30.00-120.00  103
 15  \w     94.00 176.00   1.00    6.00    --  103.24 125.00-180.00   82
 16  \w     94.00 176.00   1.00    6.00    --  103.24 125.00-150.00   82
 17  \w     94.00 176.00   1.00    6.00    --  103.24 125.00-120.00   82
 18  \w   -117.00  -8.00   1.00    2.00    --  -40.45 -77.00  90.00  109
 19  \w   -115.00 -16.00   1.00    2.00    --  -40.45 -38.00 -90.00   99
 20  \w     12.00  61.00   1.00    2.00    --   40.45  57.00-120.00   49
;
_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      0.1185816000
_diffrn_orient_matrix_UB_12      -0.0021064000
_diffrn_orient_matrix_UB_13      0.1055011000
_diffrn_orient_matrix_UB_21      -0.1235584000
_diffrn_orient_matrix_UB_22      0.1093457000
_diffrn_orient_matrix_UB_23      0.0609400000
_diffrn_orient_matrix_UB_31      -0.0790141000
_diffrn_orient_matrix_UB_32      -0.1465358000
_diffrn_orient_matrix_UB_33      0.0760050000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0201
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            8431
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.808
_diffrn_reflns_theta_min         4.121
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.745
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80033
_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    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             320
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.128
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2933
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0560P)^2^+0.1100P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1084
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2463
_reflns_number_total             2933
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02289_si_014.cif
_cod_data_source_block           y2-082
_cod_database_code               4034687
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'c h o n'
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.929
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C007(H007)
2.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00E(H00E), C00G(H00G), C00H(H00H), C00I(H00I),
 C00J(H00J), C00K(H00K), C00L(H00L)
2.d Idealised Me refined as rotating group:
 C00N(H00F,H00M,H00N)
;
_shelx_res_checksum              49411
_shelx_hkl_checksum              93486
_olex2_submission_original_sample_id 082
_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 1.545
_oxdiff_exptl_absorpt_empirical_full_min 0.879