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_4518965
_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_absolute_configuration ad
_chemical_formula_moiety         'C62 H56 N7 O2 Rh, 2(C H2 Cl2)'
_chemical_formula_sum            'C64 H60 Cl4 N7 O2 Rh'
_chemical_formula_weight         1203.90
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9513(9)
_cell_length_b                   16.5866(13)
_cell_length_c                   30.088(2)
_cell_measurement_reflns_used    9717
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.8381
_cell_measurement_theta_min      2.2067
_cell_volume                     5964.4(8)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_collection       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_molecular_graphics    'Diamond v4.6.3 (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 0.998
_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  0.0418
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            87649
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.921
_diffrn_reflns_theta_min         2.176
_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    0.515
_exptl_absorpt_correction_T_max  0.9906
_exptl_absorpt_correction_T_min  0.9146
_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    1.341
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2488
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.479
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 5573 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(5)
_refine_ls_extinction_coef       0.00096(14)
_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   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     819
_refine_ls_number_reflns         14242
_refine_ls_number_restraints     207
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0257P)^2^+3.3206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0639
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.821
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                13272
_reflns_number_total             14242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02901_si_003.cif
_cod_data_source_block           YG416D2
_cod_original_cell_volume        5964.3(8)
_cod_database_code               4518965
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.859
_shelx_estimated_absorpt_t_max   0.968
_shelx_res_checksum              61253
_shelx_hkl_checksum              14373