Bulky alkali metal cations enabled highly efficient iridium-catalyzed asymmetric hydrogenation for C–N axial chirality via dynamic kinetic resolution
Zhao, Xianghua; Chen, Xinyu; Fan, Linxian; Jiang, Yulong; Chen, Yirui; Song, Dingguo; Ling, Fei; Hu, Junyuan; Zhong, Weihui; Chemical Science  (2025) –; doi:10.1039/D5SC08462H

data_1576323
_publ_section_title
;
 Bulky alkali metal cations enabled highly efficient iridium-catalyzed
 asymmetric hydrogenation for C--N axial chirality via dynamic kinetic
 resolution
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC08462H
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H19 F N2 O'
_chemical_formula_sum            'C18 H19 F N2 O'
_chemical_formula_weight         298.35
_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
_audit_creation_date             2025-03-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-06-01 deposited with the CCDC.	2025-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.8471(2)
_cell_length_b                   8.9604(2)
_cell_length_c                   22.4164(5)
_cell_measurement_reflns_used    9950
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      68.321
_cell_measurement_theta_min      3.944
_cell_volume                     1576.17(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_environment      N~2~
_diffrn_ambient_temperature      170.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Ius3.0'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            18642
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.427
_diffrn_reflns_theta_min         3.944
_diffrn_source                   'Ius X-ray source'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              Ius
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6864
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1080 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.9114.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.103
_refine_diff_density_min         -0.171
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1139 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         2895
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0296
_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^)+(0.0418P)^2^+0.1708P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0756
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2798
_reflns_number_total             2895
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08462h2.cif
_cod_data_source_block           250319_zxh03165f
_cod_database_code               1576323
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.766
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C4(H4), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              48115
_olex2_diffrn_ambient_temperature_device 'Oxford Cryostream 800'
_olex2_submission_special_instructions 'No special instructions were received'