Enantioselective α-Fluorination and α-Chlorination of N-Acyl Pyrazoles Catalyzed by a Non-C2-Symmetric Chiral-at-Rhodium Catalyst
Grell, Yvonne; Xie, Xiulan; Ivlev, Sergei I.; Meggers, Eric; ACS Catalysis  (2021) 11396–11406; doi:10.1021/acscatal.1c02901

data_4518964
_publ_section_title
;
 Enantioselective \a-Fluorination and \a-Chlorination of N-Acyl Pyrazoles
 Catalyzed by a Non-C2-Symmetric Chiral-at-Rhodium Catalyst
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11396
_journal_page_last               11406
_journal_paper_doi               10.1021/acscatal.1c02901
_journal_year                    2021
_chemical_formula_moiety         'C46 H46 N6 Rh, F6 P'
_chemical_formula_sum            'C46 H46 F6 N6 P Rh'
_chemical_formula_weight         930.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 95.521(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7967(5)
_cell_length_b                   23.7327(15)
_cell_length_c                   22.4247(14)
_cell_measurement_reflns_used    9919
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.2838
_cell_measurement_theta_min      2.4155
_cell_volume                     4659.9(5)
_computing_cell_refinement       'APEX3 v2019.1-0 (Bruker AXS)'
_computing_data_collection       'APEX3 v2019.1-0 (Bruker AXS)'
_computing_data_reduction        'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Diamond v4.6.4 (Brandenburg, 2020)'
_computing_publication_material  'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'PHOTON 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    '0.8 mm diameter'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0669
_diffrn_reflns_av_unetI/netI     0.0611
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            72282
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.350
_diffrn_reflns_theta_min         1.944
_diffrn_source                   'microfocus X-ray tube'
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.462
_exptl_absorpt_correction_T_max  0.9867
_exptl_absorpt_correction_T_min  0.8712
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1912
_exptl_crystal_size_max          0.359
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.674
_refine_diff_density_min         -0.848
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     591
_refine_ls_number_reflns         11612
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0475
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0333P)^2^+6.3784P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0871
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8560
_reflns_number_total             11612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02901_si_002.cif
_cod_data_source_block           YG392
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4518964
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.852
_shelx_estimated_absorpt_t_max   0.975
_shelx_res_checksum              5945
_shelx_hkl_checksum              88905
_shelx_fab_checksum              7566