Catalytic asymmetric synthesis of indole-based atropisomers bearing silicon-stereogenic centers.
Liu, Si-Yi; Zhu, Zi-Qi; Chen, Fei-Xiao; Feng, Ni-Na; Ni, Shao-Fei; Shi, Feng; Chemical science 16 (2025) 21394–21403; doi:10.1039/d5sc05320j

data_1575981
_publ_section_title
;
 Catalytic asymmetric synthesis of indole-based atropisomers bearing
 silicon-stereogenic centers.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              21394
_journal_page_last               21403
_journal_paper_doi               10.1039/d5sc05320j
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C28 H27 N O3 Si'
_chemical_formula_sum            'C28 H27 N O3 Si'
_chemical_formula_weight         453.59
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-17
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-03 deposited with the CCDC.	2025-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.610(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.254(3)
_cell_length_b                   8.328(2)
_cell_length_c                   13.391(4)
_cell_measurement_reflns_used    2985
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      47.983
_cell_measurement_theta_min      2.873
_cell_volume                     1254.6(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.1383
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11581
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.939
_diffrn_reflns_theta_min         2.872
_diffrn_source_current           2.86
_diffrn_source_power             0.1995708
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.678
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.3106
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1539 before and 0.0975 after correction.
The Ratio of minimum to maximum transmission is 0.4137.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 676 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(6)
_refine_ls_extinction_coef       0.013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         4486
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1658
_refine_ls_R_factor_gt           0.0842
_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^)+(0.1347P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2107
_refine_ls_wR_factor_ref         0.2601
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.908
_reflns_Friedel_fraction_max     0.883
_reflns_number_gt                2246
_reflns_number_total             4486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05320j2.cif
_cod_data_source_block           240617sf_lsy_1
_cod_depositor_comments          'Adding full bibliography for 1575981.cif.'
_cod_original_cell_volume        1254.6(5)
_cod_database_code               1575981
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.893
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All Si(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 Si1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1A), C7(H7), C6(H6), C5(H5), C4(H4), C3(H3), C15(H15), C12(H12), C26(H26),
  C25(H25), C20(H20), C21(H21), C22(H22), C23(H23)
2.c Fitted hexagon refined as free rotating group:
 C2(C7,C6,C5,C4,C3), C10(C15,C14,C13,C12,C11)
2.d Naphthalene refined as free rotating group:
 C18(C27,C26,C25,C24,C19,C20,C21,C22,C23)
2.e Idealised Me refined as rotating group:
 C1(H1B,H1C,H1D), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              84778
_olex2_submission_special_instructions 'No special instructions were received'