Stereodivergent Synthesis of Enantioenriched Azepino[3,4,5-cd]-Indoles via Cooperative Cu/Ir-Catalyzed Asymmetric Allylic Alkylation and Intramolecular Friedel-Crafts Reaction
Xiao, Lu; Li, Bo; Xiao, Fan; Fu, Cong; Wei, Liang; Dang, Yanfeng; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical Science  (2022) –; doi:10.1039/D1SC07271D

data_1566725
_publ_section_title
;
 Stereodivergent Synthesis of Enantioenriched Azepino[3,4,5-cd]-Indoles
 via Cooperative Cu/Ir-Catalyzed Asymmetric Allylic Alkylation and
 Intramolecular Friedel-Crafts Reaction
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC07271D
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 Cl N2 O2'
_chemical_formula_sum            'C23 H23 Cl N2 O2'
_chemical_formula_weight         394.88
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-06-16 deposited with the CCDC.	2022-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.29920(10)
_cell_length_b                   18.0846(2)
_cell_length_c                   24.7440(2)
_cell_measurement_reflns_used    23801
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5640
_cell_measurement_theta_min      4.3230
_cell_volume                     4161.26(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -32.00  28.00   0.50    0.50    --    0.00 -82.00-120.00  120
  2  \w    -14.00  12.00   0.50    0.50    --    0.00 -82.00 120.00   52
  3  \w    -43.00  12.00   0.50    0.50    --    0.00 -77.00 150.00  110
  4  \w    -46.00  27.00   0.50    0.50    --    0.00 -77.00  60.00  146
  5  \w    -89.00   0.00   0.50    0.50    --    0.00 -19.00-150.00  178
  6  \w     49.00  79.00   0.50    0.50    --    0.00  38.00   0.00   60
  7  \w     81.00 183.00   0.50    2.00    --   94.60  45.00 -30.00  204
  8  \w      6.00 108.00   0.50    2.00    --   94.60 -61.00-120.00  204
  9  \w     11.00 109.00   0.50    2.00    --   94.60 -61.00 120.00  196
 10  \w     48.00  74.00   0.50    2.00    --   94.60 -30.00-150.00   52
 11  \w      5.00 122.00   0.50    2.00    --   94.60 -82.00-120.00  234
 12  \w    137.00 163.00   0.50    2.00    --   94.60  45.00 150.00   52
 13  \w     78.00 183.00   0.50    2.00    --   94.60  30.00 120.00  210
 14  \w     83.00 169.00   0.50    2.00    --   94.60  45.00   0.00  172
 15  \w     95.00 183.00   0.50    2.00    --   94.60  15.00  90.00  176
 16  \w     92.00 124.00   0.50    2.00    --   94.60  77.00  30.00   64
 17  \w    109.00 134.00   0.50    2.00    --   94.60  45.00 150.00   50
 18  \w      6.00 103.00   0.50    2.00    --   94.60 -45.00 120.00  194
 19  \w    112.00 158.00   0.50    2.00    --   94.60  45.00 -90.00   92
 20  \w      6.00  31.00   0.50    2.00    --   94.60 -30.00-150.00   50
 21  \w     80.00 136.00   0.50    2.00    --   94.60  45.00 -60.00  112
 22  \w     82.00 109.00   0.50    2.00    --   94.60  77.00-120.00   54
 23  \w     49.00 102.00   0.50    2.00    --   94.60 -30.00-120.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0426780000
_diffrn_orient_matrix_UB_12      0.0152685000
_diffrn_orient_matrix_UB_13      -0.0590675000
_diffrn_orient_matrix_UB_21      0.0726213000
_diffrn_orient_matrix_UB_22      -0.0727244000
_diffrn_orient_matrix_UB_23      -0.0174654000
_diffrn_orient_matrix_UB_31      -0.1427195000
_diffrn_orient_matrix_UB_32      -0.0416747000
_diffrn_orient_matrix_UB_33      0.0088633000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            44962
_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         73.939
_diffrn_reflns_theta_min         3.027
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.783
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57131
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       plank
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.528
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 3378 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         8320
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0737P)^2^+1.3139P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1131
_refine_ls_wR_factor_ref         0.1141
_reflns_Friedel_coverage         0.773
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                8054
_reflns_number_total             8320
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07271d3.cif
_cod_data_source_block           xl-9-104
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C46 H46 Cl2 N4 O4'
_cod_original_formula_weight         789.77
_cod_original_formula_moiety         '2(C23 H23 Cl N2 O2)'
_cod_original_formula_units_Z            4
_cod_database_code               1566725
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.695
_reflns_odcompleteness_completeness 99.98
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N009(H009), N00A(H00A)
2.b Ternary CH refined with riding coordinates:
 C00I(H00I), C00M(H00M), C00Y(H00Y), C013(H013)
2.c Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00K(H00K), C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U),
 C00X(H00X), C00Z(H00Z), C011(H011), C012(H012), C014(H014), C016(H016),
 C017(H017), C018(H018), C01B(H01M), C01C(H01N), C01F(H01I), C01G(H01R)
2.d X=CH2 refined with riding coordinates:
 C01A(H01D,H01E), C01I(H01V,H01W)
2.e Idealised Me refined as rotating group:
 C019(H01A,H01B,H01C), C01D(H01O,H01P,H01Q), C01E(H01F,H01G,H01H), C01H(H01S,
 H01T,H01U), C01J(H01J,H01K,H01L), C01K(H01X,H01Y,H)
;
_shelx_res_checksum              55445
_shelx_hkl_checksum              9926
_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 1.654
_oxdiff_exptl_absorpt_empirical_full_min 0.575