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_4034690
_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         '0.13(C19 H17 N O4)'
_chemical_formula_sum            'C38 H34 N2 O8'
_chemical_formula_weight         646.68
_chemical_name_systematic        Y-II-162
_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     iterative
_audit_creation_date             2019-07-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.551(3)
_cell_angle_gamma                90
_cell_formula_units_Z            64
_cell_length_a                   13.9277(3)
_cell_length_b                   14.1983(3)
_cell_length_c                   18.4795(4)
_cell_measurement_reflns_used    5598
_cell_measurement_temperature    294.41(10)
_cell_measurement_theta_max      72.5130
_cell_measurement_theta_min      4.0070
_cell_volume                     3421.75(14)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.41(10)
_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 0.971
_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   -108.00 -30.00   1.00    2.00    --  -40.45 -38.00 -60.00   78
  2  \w   -115.00 -17.00   1.00    2.00    --  -40.45 -38.00-150.00   98
  3  \w    -39.00  -4.00   1.00    2.00    --  -40.45 125.00  60.00   35
  4  \w    116.00 165.00   1.00    5.00    --  103.24  45.00-150.00   49
  5  \w     94.00 175.00   1.00    5.00    --  103.24 125.00 120.00   81
  6  \w     24.00 107.00   1.00    5.00    --  103.24 -94.00-150.00   83
  7  \w     65.00 118.00   1.00    5.00    --  103.24 -45.00-150.00   53
  8  \w     88.00 116.00   1.00    5.00    --  103.24-125.00  90.00   28
  9  \w     98.00 124.00   1.00    5.00    --  103.24 125.00 -60.00   26
 10  \w     54.00  80.00   1.00    5.00    --  103.24 -30.00-180.00   26
 11  \w     27.00 130.00   1.00    5.00    --  103.24 -30.00  30.00  103
;
_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      -0.0164416000
_diffrn_orient_matrix_UB_12      -0.0111786000
_diffrn_orient_matrix_UB_13      0.0777727000
_diffrn_orient_matrix_UB_21      -0.0723886000
_diffrn_orient_matrix_UB_22      -0.0838215000
_diffrn_orient_matrix_UB_23      -0.0330965000
_diffrn_orient_matrix_UB_31      0.0918855000
_diffrn_orient_matrix_UB_32      -0.0679624000
_diffrn_orient_matrix_UB_33      0.0280118000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            13598
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.689
_diffrn_reflns_theta_min         3.454
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.062
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86358
_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    1.336
_exptl_crystal_description       block
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.034
_refine_ls_extinction_coef       0.00124(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         6607
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0669P)^2^+0.6079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1201
_refine_ls_wR_factor_ref         0.1297
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5472
_reflns_number_total             6607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02289_si_002.cif
_cod_data_source_block           y-ii-162
_cod_original_formula_sum        '2(C19 H17 N O4)'
_cod_database_code               4034690
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N '
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.901
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00B(H00B), C00K(H00K)
2.b Aromatic/amide H refined with riding coordinates:
 N002(H002), N003(H003), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T),
 C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C012(H012), C013(H013), C014(H014), C015(H015), C016(H016),
 C017(H017), C018(H018)
2.c Idealised Me refined as rotating group:
 C019(H01A,H01B,H01C), C01A(H01D,H01E,H01F), C01B(H01G,H01H,H01I), C01C(H01J,
 H01K,H01L)
;
_olex2_submission_original_sample_id Y-II-162
_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 1.219
_oxdiff_exptl_absorpt_empirical_full_min 0.833