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_4519298
_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 ad
_chemical_formula_moiety         'C39 H39 Cu N4 O2, C H Cl3, 2(B F4)'
_chemical_formula_sum            'C40 H40 B2 Cl3 Cu F8 N4 O2'
_chemical_formula_weight         952.27
_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
_audit_creation_date             2021-09-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.070(2)
_cell_length_b                   14.339(3)
_cell_length_c                   21.988(4)
_cell_measurement_reflns_used    11320
_cell_measurement_temperature    123
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      3.10
_cell_volume                     4120.8(13)
_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    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123.15
_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           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0887
_diffrn_reflns_av_unetI/netI     0.0573
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            35667
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.550
_diffrn_reflns_theta_min         3.117
_exptl_absorpt_coefficient_mu    0.803
_exptl_absorpt_correction_T_max  0.930
_exptl_absorpt_correction_T_min  0.788
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'REQAB (Rigaku, 1998)'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.309
_refine_diff_density_min         -0.897
_refine_diff_density_rms         0.102
_refine_ls_abs_structure_details
;
 Flack x determined using 2763 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         9455
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0659
_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^)+(0.1516P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1912
_refine_ls_wR_factor_ref         0.2042
_reflns_Friedel_coverage         0.803
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7417
_reflns_number_total             9455
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05500_si_002.cif
_cod_data_source_block           20200915-1
_cod_database_code               4519298
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.740
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C31(H31), C47(H47), C59(H59)
2.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C37(H37A,H37B), C43(H43A,H43B), C48(H48A,H48B), C49(H49A,H49B)
2.c Me refined with riding coordinates:
 C53(H53A,H53B,H53C)
2.d Aromatic/amide H refined with riding coordinates:
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C27(H27), C29(H29),
 C30(H30), C32(H32), C36(H36), C39(H39), C40(H40), C41(H41), C45(H45), C51(H51),
  C54(H54), C55(H55), C58(H58)
2.e Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              25599
_shelx_hkl_checksum              14847
_olex2_submission_special_instructions 'No special instructions were received'