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_1566726
_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             2021-03-24
_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            16
_cell_length_a                   9.11893(5)
_cell_length_b                   17.37833(10)
_cell_length_c                   50.2087(3)
_cell_measurement_reflns_used    62968
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5650
_cell_measurement_theta_min      2.6950
_cell_volume                     7956.66(8)
_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    -33.00  31.00   0.50    0.50    --    0.00 -82.00-150.00  128
  2  \w     28.00  89.00   0.50    0.50    --    0.00  57.00-120.00  122
  3  \w    -32.00  30.00   0.50    0.50    --    0.00 -82.00 150.00  124
  4  \w    -13.00  13.00   0.50    0.50    --    0.00 -82.00 -30.00   52
  5  \w     -6.00  20.00   0.50    0.50    --    0.00 -82.00  60.00   52
  6  \w    -76.00 -45.00   0.50    0.50    --    0.00 -57.00 -60.00   62
  7  \w    -14.00  21.00   0.50    0.50    --    0.00 -57.00 -60.00   70
  8  \w      6.00 126.00   0.50    1.00    --   94.60 -82.00 150.00  240
  9  \w      5.00 114.00   0.50    1.00    --   94.60 -77.00  30.00  218
 10  \w     78.00 108.00   0.50    1.00    --   94.60  30.00 -30.00   60
 11  \w      5.00  57.00   0.50    1.00    --   94.60 -82.00  60.00  104
 12  \w     76.00 102.00   0.50    1.00    --   94.60 -82.00  60.00   52
 13  \w     78.00 179.00   0.50    1.00    --   94.60  30.00   0.00  202
 14  \w     80.00 157.00   0.50    1.00    --   94.60  30.00 -60.00  154
 15  \w      5.00 102.00   0.50    1.00    --   94.60 -82.00 -60.00  194
 16  \w     71.00 184.00   0.50    1.00    --   94.60  61.00  30.00  226
 17  \w     83.00 109.00   0.50    1.00    --   94.60 -82.00  90.00   52
 18  \w     20.00  77.00   0.50    1.00    --   94.60 -82.00  90.00  114
 19  \w     90.00 163.00   0.50    1.00    --   94.60  82.00 120.00  146
 20  \w     53.00 102.00   0.50    1.00    --   94.60 -82.00-150.00   98
 21  \w     60.00 125.00   0.50    1.00    --   94.60 -82.00-120.00  130
 22  \w     72.00  97.00   0.50    1.00    --   94.60 -82.00   0.00   50
 23  \w     71.00 100.00   0.50    1.00    --   94.60  61.00-150.00   58
 24  \w     79.00 121.00   0.50    1.00    --   94.60  77.00-150.00   84
 25  \w     10.00 109.00   0.50    1.00    --   94.60 -61.00 150.00  198
;
_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      -0.0365956000
_diffrn_orient_matrix_UB_12      -0.0800903000
_diffrn_orient_matrix_UB_13      -0.0113541000
_diffrn_orient_matrix_UB_21      0.1490469000
_diffrn_orient_matrix_UB_22      -0.0304619000
_diffrn_orient_matrix_UB_23      0.0098480000
_diffrn_orient_matrix_UB_31      -0.0705972000
_diffrn_orient_matrix_UB_32      -0.0227667000
_diffrn_orient_matrix_UB_33      0.0267469000
_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  0.0429
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            93510
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.023
_diffrn_reflns_theta_min         2.691
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.865
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79294
_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    1.319
_exptl_crystal_description       prism
_exptl_crystal_F_000             3328
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.766
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 6661 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1037
_refine_ls_number_reflns         15947
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0486
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0747P)^2^+4.9281P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1328
_refine_ls_wR_factor_ref         0.1332
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                15663
_reflns_number_total             15947
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07271d3.cif
_cod_data_source_block           20210324_xl-9-62
_cod_original_cell_volume        7956.67(8)
_cod_database_code               1566726
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.707
_shelx_estimated_absorpt_t_min   0.605
_reflns_odcompleteness_completeness 99.97
_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. Restrained distances
 N00J-H00J = N00H-H00H = N00C-H00C = N00G-H00G
 0.85 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C00L(H00L), C00O(H00O), C015(H015), C01G(H01G), C01T(H01T), C01V(H01V),
 C023(H023), C02C(H02W)
3.b Aromatic/amide H refined with riding coordinates:
 C00Q(H00Q), C00U(H00U), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011),
 C013(H013), C017(H017), C019(H019), C01B(H01B), C01E(H01E), C01K(H01K),
 C01O(H01O), C01Q(H01Q), C01R(H01R), C01W(H01W), C01X(H01X), C01Y(H01Y),
 C020(H020), C022(H022), C024(H024), C027(H027), C028(H028), C029(H029),
 C02A(H02U), C02B(H02V), C02F(H3), C02J(H02L), C02K(H02Z), C02N(H5), C02P(H6),
 C02R(H7), C02S(H02), C02T(H1), C02V(H8), C02X(H9)
3.c X=CH2 refined with riding coordinates:
 C02M(H02M,H02N), C02O(H02D,H02E), C02Y(H10,HC), C030(H03D,H03E)
3.d Idealised Me refined as rotating group:
 C021(H02I,H02J,H02K), C02D(H02A,H02B,H02C), C02G(H02X,H02Y,H), C02H(H4,HA,HB),
  C02Q(H02F,H02G,H02H), C02U(H02O,H02P,H02Q), C02W(H02R,H02S,H02T), C02Z(H2,HD,
 HE), C031(H03I,H03J,H03K), C032(H03F,H03G,H03H), C033(H03L,H03M,H03N),
 C034(H03A,H03B,H03C)
;
_shelx_res_checksum              83074
_shelx_hkl_checksum              93989
_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 3.513
_oxdiff_exptl_absorpt_empirical_full_min 0.686