Catalytic asymmetric C-7 Friedel-Crafts reaction of 4-aminoindoles: construction of <i>N</i>-substituted quaternary carbon atoms.
Liu, Shenggui; Ye, Hang; He, Hualing; Organic & biomolecular chemistry 23 (2025) 5339–5342; doi:10.1039/d5ob00558b

data_7160530
_publ_section_title
;
 Catalytic asymmetric C-7 Friedel-Crafts reaction of 4-aminoindoles:
 construction of <i>N</i>-substituted quaternary carbon atoms.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5339
_journal_page_last               5342
_journal_paper_doi               10.1039/d5ob00558b
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C30 H26 Cl N3 O), C4 H8 O2'
_chemical_formula_sum            'C64 H60 Cl2 N6 O4'
_chemical_formula_weight         1048.08
_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
_audit_creation_date             2025-04-15
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7205)
;
_audit_update_record
;
2025-04-26 deposited with the CCDC.	2025-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.5370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.47670(10)
_cell_length_b                   34.4041(2)
_cell_length_c                   9.54320(10)
_cell_measurement_reflns_used    44504
_cell_measurement_temperature    159.99(10)
_cell_measurement_theta_max      74.8220
_cell_measurement_theta_min      2.5520
_cell_volume                     2744.65(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      159.99(10)
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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    -72.00  17.00   0.50    0.05    --    0.00 -68.00 131.00  178
  2  \w    -17.00  72.00   0.50    0.05    --    0.00  68.00 -95.00  178
  3  \w   -172.00 -83.00   0.50    0.14    -- -100.00 -68.00 131.00  178
  4  \w   -117.00 -28.00   0.50    0.14    -- -100.00  68.00 -95.00  178
  5  \w     28.00 117.00   0.50    0.14    --  100.00 -68.00 131.00  178
  6  \w     83.00 172.00   0.50    0.14    --  100.00  68.00 -95.00  178
  7  \w    -13.00  72.00   0.50    0.05    --    0.00  57.00  60.00  170
  8  \w    -71.00   8.00   0.50    0.05    --    0.00 -38.00-150.00  158
  9  \w    -13.00  72.00   0.50    0.05    --    0.00  57.00 -30.00  170
 10  \w   -172.00 -86.00   0.50    0.14    -- -100.00 -61.00-150.00  172
 11  \w   -172.00 -86.00   0.50    0.14    -- -100.00 -61.00 150.00  172
 12  \w   -108.00 -27.00   0.50    0.14    -- -100.00  15.00 120.00  162
 13  \w   -109.00 -28.00   0.50    0.14    -- -100.00  45.00 -90.00  162
 14  \w   -172.00 -92.00   0.50    0.14    -- -100.00 -30.00 -30.00  160
 15  \w   -172.00 -92.00   0.50    0.14    -- -100.00 -30.00  30.00  160
 16  \w   -108.00 -28.00   0.50    0.14    -- -100.00  30.00 120.00  160
 17  \w   -172.00 -79.00   0.50    0.14    -- -100.00 -77.00-150.00  186
 18  \w   -172.00 -91.00   0.50    0.14    -- -100.00 -45.00   0.00  162
 19  \w   -172.00 -91.00   0.50    0.14    -- -100.00 -45.00  30.00  162
 20  \w   -121.00 -28.00   0.50    0.14    -- -100.00  77.00   0.00  186
 21  \w   -172.00 -86.00   0.50    0.14    -- -100.00 -61.00  30.00  172
 22  \w   -172.00 -91.00   0.50    0.14    -- -100.00 -45.00  90.00  162
 23  \w     92.00 173.00   0.50    0.14    --  100.00  15.00-150.00  162
 24  \w     92.00 173.00   0.50    0.14    --  100.00  15.00  30.00  162
 25  \w     92.00 172.00   0.50    0.14    --  100.00  30.00 150.00  160
 26  \w     91.00 172.00   0.50    0.14    --  100.00  45.00  60.00  162
 27  \w    -72.00  48.00   0.50    0.05    --    0.00   0.00  30.00  240
 28  \w     -7.00  74.00   0.50    0.05    --    0.00  19.00-120.00  162
 29  \w     -7.00  74.00   0.50    0.05    --    0.00  19.00  90.00  162
 30  \w    -21.00  72.00   0.50    0.05    --    0.00  77.00-180.00  186
 31  \w     91.00 126.00   0.50    0.14    --  100.00  45.00-120.00   70
 32  \w     28.00 109.00   0.50    0.14    --  100.00 -94.00  60.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            52553
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.151
_diffrn_reflns_theta_min         2.569
_exptl_absorpt_coefficient_mu    1.496
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85552
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 4909 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(4)
_refine_ls_extinction_coef       0.0015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         10988
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0728P)^2^+0.5569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1127
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                10629
_reflns_number_total             10988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00558b2.cif
_cod_data_source_block           037684_hhl3-101-160-a
_cod_depositor_comments          'Adding full bibliography for 7160530.cif.'
_cod_database_code               7160530
_shelx_shelxl_version_number     2019/3
_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
 N1-H1
 0.9 with sigma of 0.02
 N4-H4A
 0.9 with sigma of 0.02
 N6-H6A
 0.9 with sigma of 0.02
 N5-H5A
 0.9 with sigma of 0.02
 N3-H3
 0.9 with sigma of 0.02
 N2-H2
 0.9 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C54(H54A,H54B), C63(H63A,H63B)
3.b Aromatic/amide H refined with riding coordinates:
 C44(H44), C48(H48), C18(H18), C43(H43), C22(H22), C19(H19), C14(H14),
 C16(H16), C13(H13), C21(H21), C3(H3A), C33(H33), C20(H20), C56(H56), C15(H15),
 C37(H37), C45(H45), C36(H36), C50(H50), C46(H46), C34(H34), C49(H49), C26(H26),
  C4(H4), C7(H7), C57(H57), C35(H35), C5(H5), C6(H6), C51(H51), C27(H27),
 C52(H52), C29(H29), C28(H28), C59(H59), C58(H58)
3.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C53(H53A,H53B,H53C), C62(H62A,H62B,H62C), C64(H64A,H64B,
 H64C)
;
_shelx_res_checksum              74299
_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 1.355
_oxdiff_exptl_absorpt_empirical_full_min 0.808