Highly enantioselective synthesis of functionalized azepino[1,2-a]indoles via NHC-catalyzed [3+4] annulation
Zhu, Shi-Ya; Zhang, Yuanzheng; Chen, Xin-Fa; Huang, Jun; Shi, Shihui; Hui, Xin-Ping; Chemical Communications  (2019) –; doi:10.1039/C9CC01444F

data_7123146
_publ_section_title
;
 Highly enantioselective synthesis of functionalized azepino[1,2-a]indoles
 via NHC-catalyzed [3+4] annulation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC01444F
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H20 Br N O6'
_chemical_formula_sum            'C24 H20 Br N O6'
_chemical_formula_weight         498.32
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3'
_symmetry_space_group_name_Hall  'R 3'
_symmetry_space_group_name_H-M   'R 3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2019-02-18 deposited with the CCDC.    2019-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            9
_cell_length_a                   23.787(3)
_cell_length_b                   23.787(3)
_cell_length_c                   10.1900(18)
_cell_measurement_reflns_used    815
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.5750
_cell_measurement_theta_min      4.0750
_cell_volume                     4993.3(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -50.00   56.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  -77.0000  -60.0000 106

  2 omega   37.00   63.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  178.0000  -30.0000 26
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0022060000
_diffrn_orient_matrix_UB_12      -0.0305962000
_diffrn_orient_matrix_UB_13      0.0102890000
_diffrn_orient_matrix_UB_21      0.0342612000
_diffrn_orient_matrix_UB_22      0.0148158000
_diffrn_orient_matrix_UB_23      -0.0038198000
_diffrn_orient_matrix_UB_31      0.0021868000
_diffrn_orient_matrix_UB_32      0.0053328000
_diffrn_orient_matrix_UB_33      0.0686401000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1185
_diffrn_reflns_av_unetI/netI     0.1989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            3694
_diffrn_reflns_theta_full        25.99
_diffrn_reflns_theta_max         25.99
_diffrn_reflns_theta_min         3.29
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.893
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.06573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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    1.491
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2286
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.859
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         2468
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.859
_refine_ls_R_factor_all          0.1414
_refine_ls_R_factor_gt           0.0635
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0211P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1011
_refine_ls_wR_factor_ref         0.1415
_reflns_number_gt                1045
_reflns_number_total             2468
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c9cc01444f2.cif
_cod_data_source_block           zhuishiy_0319
_cod_database_code               7123146
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C16(H16), C17(H17), C19(H19),
 C20(H20)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C24(H24A,H24B,H24C)
;
_olex2_date_sample_data_collection 2018-03-21
_olex2_submission_special_instructions 'No special instructions were received'