A π–Cu(II)−π Complex as an Extremely Active Catalyst for Enantioselective α-Halogenation of N-Acyl-3,5-dimethylpyrazoles
Nishimura, Kazuki; Wang, Yanzhao; Ogura, Yoshihiro; Kumagai, Jun; Ishihara, Kazuaki; ACS Catalysis 12 (2022) 1012–1017; doi:10.1021/acscatal.1c05500

data_4519299
_publ_section_title
;
 A \p--Cu(II)&#x2212;\p Complex as an Extremely Active Catalyst for
 Enantioselective \a-Halogenation of N-Acyl-3,5-dimethylpyrazoles
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              1012
_journal_page_last               1017
_journal_paper_doi               10.1021/acscatal.1c05500
_journal_volume                  12
_journal_year                    2022
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C41 H48 Cu F6 N4 O10 S2'
_chemical_formula_sum            'C41 H48 Cu F6 N4 O10 S2'
_chemical_formula_weight         998.51
_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
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   14.6616(11)
_cell_length_b                   15.7092(13)
_cell_length_c                   19.6198(16)
_cell_measurement_reflns_used    16433
_cell_measurement_temperature    123
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      3.10
_cell_volume                     4518.9(6)
_computing_cell_refinement       'CrystalClear-SM Expert 2.1 b29'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b29 (Rigaku, 2013)'
_computing_data_reduction        'CrystalClear-SM Expert 2.1 b29'
_computing_molecular_graphics    'CrystalStructure 4.2.2'
_computing_publication_material  'CrystalStructure 4.2.2 (Rigaku, 2016)'
_computing_structure_refinement  'SHELXL Version 2016/4 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123
_diffrn_detector_area_resol_mean 5.814
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.1213
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            38289
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.471
_diffrn_reflns_theta_min         3.067
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.660
_exptl_absorpt_correction_T_max  0.876
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2068.00
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.200
_refine_diff_density_max         1.16
_refine_diff_density_min         -0.66
_refine_ls_abs_structure_details
;
 Flack x determined using 3948 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_number_parameters     605
_refine_ls_number_reflns         10264
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0411
_refine_ls_shift/su_max          0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0670P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1084
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                9524
_reflns_number_total             10264
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            cs1c05500_si_003.cif
_cod_data_source_block           KN5-8126-1
_cod_database_code               4519299
_shelx_res_checksum              32270
_shelx_hkl_checksum              16015