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_1566724
_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      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-28
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-06-16 deposited with the CCDC.	2022-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.1060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.60640(10)
_cell_length_b                   7.93310(10)
_cell_length_c                   13.74800(10)
_cell_measurement_reflns_used    12979
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.7700
_cell_measurement_theta_min      3.2680
_cell_volume                     1028.094(19)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -20.00  24.00   0.50    0.50    --    0.00 -82.00  60.00   88
  2  \w     85.00 111.00   0.50    0.50    --   32.00  70.00 116.08   52
  3  \w    -13.00  57.00   0.50    0.50    --   32.00 -69.00 -48.41  140
  4  \w    -57.00 -18.00   0.50    0.50    --   32.00 -69.00 -48.41   78
  5  \w      7.00  37.00   0.50    0.50    --   32.00  70.00 116.08   60
  6  \w     13.00  55.00   0.50    0.50    --   40.00  72.00-107.43   84
  7  \w     26.00  57.00   0.50    0.50    --   52.00  72.00 -69.04   62
  8  \w     31.00  56.00   0.50    0.50    --   56.00  74.00  27.58   50
  9  \w     32.00  75.00   0.50    0.50    --   56.00  75.00 -44.34   86
 10  \w     32.00  66.00   0.50    0.50    --   60.00  75.00 105.31   68
 11  \w     34.00  64.00   0.50    0.50    --   60.00  75.00  53.74   60
 12  \w     37.00  71.00   0.50    0.50    --   64.00  74.00 164.62   68
 13  \w     36.00  64.00   0.50    0.50    --   64.00  74.00 -19.64   56
 14  \w     37.00  72.00   0.50    0.50    --   64.00  73.00 135.35   70
 15  \w     84.00 155.00   0.50    0.50    --   68.00  70.00-136.79  142
 16  \w     42.00  76.00   0.50    0.50    --   68.00  70.00-136.79   68
 17  \w    110.00 161.00   0.50    0.50    --   72.00  68.00 -53.12  102
 18  \w     48.00  81.00   0.50    0.50    --   72.00  68.00 -53.12   66
 19  \w    118.00 159.00   0.50    0.50    --   76.00  67.00-110.19   82
 20  \w     51.00  92.00   0.50    0.50    --   76.00  67.00-110.19   82
 21  \w    115.00 167.00   0.50    0.50    --   84.00  70.00   4.85  104
 22  \w     58.00 103.00   0.50    0.50    --   84.00  70.00   4.85   90
 23  \w      8.00 117.00   0.50    0.50    --   94.60 -61.00 150.00  218
 24  \w    113.00 184.00   0.50    0.50    --   94.60  82.00 120.00  142
 25  \w     67.00 154.00   0.50    0.50    --   94.60  75.00  12.63  174
 26  \w     71.00 123.00   0.50    0.50    --   94.60  61.00 -60.00  104
 27  \w      6.00 125.00   0.50    0.50    --   94.60 -82.00 150.00  238
 28  \w     14.00 116.00   0.50    0.50    --   94.60 -61.00   0.00  204
 29  \w     68.00 100.00   0.50    0.50    --   94.60  69.00  48.74   64
 30  \w    134.00 183.00   0.50    0.50    --   94.60  64.00-143.96   98
 31  \w     71.00 126.00   0.50    0.50    --   94.60  61.00 120.00  110
 32  \w     88.00 123.00   0.50    0.50    --   94.60 -82.00-150.00   70
 33  \w     86.00 162.00   0.50    0.50    --   94.60  45.00-150.00  152
 34  \w     69.00 119.00   0.50    0.50    --   94.60 -82.00 -30.00  100
 35  \w     40.00  65.00   0.50    0.50    --   94.60 -82.00 -30.00   50
 36  \w     66.00 173.00   0.50    0.50    --   94.60  75.00-103.51  214
 37  \w    154.00 182.00   0.50    0.50    --   94.60  61.00 150.00   56
 38  \w     71.00 100.00   0.50    0.50    --   94.60  61.00-180.00   58
 39  \w     71.00 142.00   0.50    0.50    --   94.60  61.00 150.00  142
 40  \w     68.00 174.00   0.50    0.50    --   94.60  70.00  79.89  212
 41  \w     71.00 149.00   0.50    0.50    --   94.60  61.00 -30.00  156
 42  \w    156.00 182.00   0.50    0.50    --   94.60  75.00  12.63   52
 43  \w     68.00 183.00   0.50    0.50    --   94.60  72.00  59.49  230
 44  \w     70.00 124.00   0.50    0.50    --   94.60  64.00-143.96  108
 45  \w     76.00 105.00   0.50    0.50    --   94.60 -82.00  60.00   58
 46  \w     71.00 160.00   0.50    0.50    --   94.60  59.00  -6.12  178
;
_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      0.1589466000
_diffrn_orient_matrix_UB_12      0.0406397000
_diffrn_orient_matrix_UB_13      0.0098535000
_diffrn_orient_matrix_UB_21      -0.0115405000
_diffrn_orient_matrix_UB_22      -0.0302235000
_diffrn_orient_matrix_UB_23      -0.1119845000
_diffrn_orient_matrix_UB_31      -0.0363132000
_diffrn_orient_matrix_UB_32      0.1874034000
_diffrn_orient_matrix_UB_33      -0.0201836000
_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  0.0516
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            20449
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.964
_diffrn_reflns_theta_min         3.276
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.805
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47100
_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_density_diffrn    1.276
_exptl_crystal_description       plate
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1728 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.012(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         4034
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0534P)^2^+0.1498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0902
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                3930
_reflns_number_total             4034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07271d3.cif
_cod_data_source_block           20201208_xl-8-115
_cod_database_code               1566724
_shelx_shelxl_version_number     2018/3
_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:
 C00F(H00F), C00K(H00K)
2.b Aromatic/amide H refined with riding coordinates:
 C009(H009), C00C(H00C), C00E(H00E), C00G(H00G), C00H(H00H), C00L(H00L),
 C00N(H00N), C00P(H00P), C00Q(H00Q)
2.c X=CH2 refined with riding coordinates:
 C00R(H00O,H00R)
2.d Idealised Me refined as rotating group:
 C00J(H00A,H00B,H00D), C00O(H00I,H00J,H00M), C00S(H00S,H00T,H00U)
;
_shelx_res_checksum              15074
_shelx_hkl_checksum              95316
_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 2.031
_oxdiff_exptl_absorpt_empirical_full_min 0.583