Monodentate/bidentate chiral Ph/Py-NO ligands: an unexpected switch of enantioselectivity in Friedel–Crafts alkylation of indoles and 2,3-dioxopyrrolidines
Lou, Jing; Zhu, Xian-Qiao; Pan, Di-Cheng; Liu, De-Wu; Jing, Hui-Xian; Liu, Xiong-Li; Zhang, Wen-Jing; Cen, Hong-Xing; Deng, Guo-Dong; New Journal of Chemistry 49 (2025) 17335–17349; doi:10.1039/D5NJ02472B

data_7063990
_publ_section_title
;
 Monodentate/bidentate chiral Ph/Py-NO ligands: an unexpected switch of
 enantioselectivity in Friedel--Crafts alkylation of indoles and
 2,3-dioxopyrrolidines
;
_journal_issue                   39
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              17335
_journal_page_last               17349
_journal_paper_doi               10.1039/D5NJ02472B
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H16 Br N3 O2, H2 O'
_chemical_formula_sum            'C17 H18 Br N3 O3'
_chemical_formula_weight         392.25
_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             2024-10-11
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-04-21 deposited with the CCDC.	2025-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.20000(10)
_cell_length_b                   10.2862(2)
_cell_length_c                   24.1774(4)
_cell_measurement_reflns_used    3996
_cell_measurement_temperature    219.99(10)
_cell_measurement_theta_max      73.5240
_cell_measurement_theta_min      3.6040
_cell_volume                     1790.59(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      219.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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    -65.00  34.00   1.00    1.13    --  -40.73  38.00  60.00   99
  2  \w     16.00 115.00   1.00    1.13    --   40.73  38.00-150.00   99
  3  \w     23.00  97.00   1.00    1.13    --   40.73-125.00  60.00   74
  4  \w     32.00 138.00   1.00    2.00    --  107.58 -77.00  30.00  106
  5  \w     82.00 170.00   1.00    2.00    --  107.58  45.00 150.00   88
  6  \w     37.00 116.00   1.00    2.00    --  107.58 -45.00-180.00   79
  7  \w     92.00 140.00   1.00    2.00    --  107.58 -77.00  90.00   48
  8  \w     31.00  66.00   1.00    2.00    --  107.58 -77.00  90.00   35
  9  \w    145.00 176.00   1.00    2.00    --  107.58  77.00 -30.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0274077000
_diffrn_orient_matrix_UB_12      -0.0975626000
_diffrn_orient_matrix_UB_13      -0.0476479000
_diffrn_orient_matrix_UB_21      -0.0476145000
_diffrn_orient_matrix_UB_22      -0.1072719000
_diffrn_orient_matrix_UB_23      0.0421633000
_diffrn_orient_matrix_UB_31      -0.2067775000
_diffrn_orient_matrix_UB_32      0.0375780000
_diffrn_orient_matrix_UB_33      -0.0033792000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            6892
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.696
_diffrn_reflns_theta_min         3.656
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.300
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63188
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.581
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1259 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         3513
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0627P)^2^+0.1352P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1121
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.952
_reflns_number_gt                3290
_reflns_number_total             3513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj02472b2.cif
_cod_data_source_block           exp_5637
_cod_depositor_comments          'Adding full bibliography for 7063990.cif.'
_cod_database_code               7063990
_shelx_shelxl_version_number     2018/3
_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 O(H,H) groups
2.a Free rotating group:
 O3(H3C,H3D)
2.b Ternary CH refined with riding coordinates:
 C1(H1), C12(H12)
2.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
2.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16), C17(H17)
;
_shelx_res_checksum              21020
_olex2_date_sample_data_collection 2024-10-11
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.827
_oxdiff_exptl_absorpt_empirical_full_min 0.630