Atroposelective synthesis of axially chiral indolizinylpyrroles by catalytic asymmetric Paal-Knorr reaction.
Zhan, Wenyan; Hu, Jiameng; Chen, Xiaoyun; Luo, Gen; Song, Xiaoxiao; Chemical communications (Cambridge, England) 60 (2024) 14984–14987; doi:10.1039/d4cc04678a

data_7133986
_publ_section_title
;
 Atroposelective synthesis of axially chiral indolizinylpyrroles by
 catalytic asymmetric Paal-Knorr reaction.
;
_journal_issue                   100
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14984
_journal_page_last               14987
_journal_paper_doi               10.1039/d4cc04678a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H22 Br2 Cl N3 O2'
_chemical_formula_sum            'C26 H22 Br2 Cl N3 O2'
_chemical_formula_weight         603.73
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-05-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-05-13 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9201(4)
_cell_length_b                   12.9585(5)
_cell_length_c                   20.1488(7)
_cell_measurement_reflns_used    9626
_cell_measurement_temperature    296.15(10)
_cell_measurement_theta_max      72.142
_cell_measurement_theta_min      6.032
_cell_volume                     2590.12(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      296.15(10)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0775
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            83602
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.539
_diffrn_reflns_theta_min         4.969
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.146
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.2831
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1716 before and 0.1139 after correction.
The Ratio of minimum to maximum transmission is 0.3757.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.820
_refine_diff_density_min         -0.675
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Flack x determined using 2028 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.112(6)
_refine_ls_extinction_coef       0.0119(10)
_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   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         5083
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0473
_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^)+(0.0781P)^2^+1.3797P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1267
_refine_ls_wR_factor_ref         0.1287
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                4832
_reflns_number_total             5083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04678a2.cif
_cod_data_source_block           20240509d
_cod_depositor_comments          'Adding full bibliography for 7133986.cif.'
_cod_database_code               7133986
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.554
_shelx_estimated_absorpt_t_min   0.458
_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. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim O1 \\sim O2 \\sim C20A \\sim O1A \\sim O2A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Same fragment restrains
{C19, C20A, O1A, O2A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C19, C20, O1, O2}
4. Others
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(O1A)=Sof(O2A)=1-FVAR(1)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(O1)=Sof(O2)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C22(H22), C24(H24), C25(H25), C26(H26)
5.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C20(H20A,H20B,
 H20C), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              57702
_shelx_hkl_checksum              36905
_olex2_submission_special_instructions 'No special instructions were received'