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_4034691
_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 O5'
_chemical_formula_sum            'C20 H14 N O5'
_chemical_formula_weight         348.32
_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   mixed
_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                115.040(5)
_cell_angle_beta                 102.168(4)
_cell_angle_gamma                97.486(3)
_cell_formula_units_Z            2
_cell_length_a                   7.7017(3)
_cell_length_b                   10.8099(5)
_cell_length_c                   11.7377(6)
_cell_measurement_reflns_used    5112
_cell_measurement_temperature    296.70(17)
_cell_measurement_theta_max      72.8020
_cell_measurement_theta_min      4.2970
_cell_volume                     838.48(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      296.70(17)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.958
_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    1.50    --  -40.32  38.00 -30.00   99
  2  \w    -68.00  33.00   1.00    1.50    --  -40.32  57.00-180.00  101
  3  \w    -92.00  -2.00   1.00    1.50    --  -40.32 125.00-120.00   90
  4  \w   -112.00 -12.00   1.00    1.50    --  -40.32 -57.00  30.00  100
  5  \w     30.00 117.00   1.00    3.00    --  103.24-125.00-180.00   87
  6  \w     74.00 176.00   1.00    3.00    --  103.24  61.00 -30.00  102
  7  \w     27.00 136.00   1.00    3.00    --  103.24 -77.00 150.00  109
  8  \w     21.00 109.00   1.00    3.00    --  103.24 -94.00-120.00   88
  9  \w     31.00 132.00   1.00    3.00    --  103.24 -61.00   0.00  101
 10  \w     30.00 129.00   1.00    3.00    --  103.24 -45.00 -30.00   99
 11  \w     94.00 176.00   1.00    3.00    --  103.24 125.00  60.00   82
 12  \w     27.00 132.00   1.00    3.00    --  103.24 -30.00-150.00  105
 13  \w     24.00 111.00   1.00    3.00    --  103.24-102.00   2.00   87
 14  \w     94.00 176.00   1.00    3.00    --  103.24 125.00-180.00   82
 15  \w     15.00 178.00   1.00    3.00    --  103.24   0.00 120.00  163
 16  \w   -112.00 -12.00   1.00    1.50    --  -40.32 -57.00 -60.00  100
 17  \w   -112.00 -12.00   1.00    1.50    --  -40.32 -57.00-150.00  100
 18  \w      8.00 116.00   1.00    1.50    --   40.32  77.00 150.00  108
;
_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      0.0948767000
_diffrn_orient_matrix_UB_12      -0.0662986000
_diffrn_orient_matrix_UB_13      0.0810544000
_diffrn_orient_matrix_UB_21      -0.0528524000
_diffrn_orient_matrix_UB_22      0.0988090000
_diffrn_orient_matrix_UB_23      0.1200566000
_diffrn_orient_matrix_UB_31      -0.1811542000
_diffrn_orient_matrix_UB_32      -0.1104676000
_diffrn_orient_matrix_UB_33      -0.0449222000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0127
_diffrn_reflns_av_unetI/netI     0.0108
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8898
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.648
_diffrn_reflns_theta_min         4.353
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75559
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       block
_exptl_crystal_F_000             362
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3206
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0724P)^2^+0.1139P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1148
_refine_ls_wR_factor_ref         0.1190
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2889
_reflns_number_total             3206
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02289_si_011.cif
_cod_data_source_block           y2-081
_cod_original_cell_volume        838.48(7)
_cod_database_code               4034691
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N '
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.921
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H00A of C00O
 At 1.2 times of:
  H00G of C00G, H008 of C008, H00F of C00F, H00K of C00K, H009 of C009, H00M
  of C00M, H00P of C00P, H00N of C00N, H00L of C00L
2.a Ternary CH refined with riding coordinates:
 C009(H009)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00F(H00F), C00G(H00G), C00K(H00K), C00L(H00L), C00M(H00M),
 C00N(H00N), C00P(H00P)
2.c Idealised Me refined as rotating group:
 C00Q(H00D,H00E,H00H)
2.d Idealised tetrahedral OH refined as rotating group:
 C00O(H00A)
;
_shelx_res_checksum              13727
_shelx_hkl_checksum              94786
_olex2_submission_original_sample_id 081
_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 1.346
_oxdiff_exptl_absorpt_empirical_full_min 0.843