Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C‒H Amidation for the Synthesis of Chiral Sulfoxides
Liu, Wentan; Yang, Wu; Zhu, Jiefeng; Guo, Yonghong; Wang, Na; Ke, Jie; Yu, Peiyuan; He, Chuan; ACS Catalysis 10 (2020) 7207–7215; doi:10.1021/acscatal.0c02109

data_4517775
_publ_section_title
;
 Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C--H Amidation for
 the Synthesis of Chiral Sulfoxides
;
_journal_issue                   13
_journal_name_full               'ACS Catalysis'
_journal_page_first              7207
_journal_page_last               7215
_journal_paper_doi               10.1021/acscatal.0c02109
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety         'C26 H42 Cl4 Ir2'
_chemical_formula_sum            'C26 H42 Cl4 Ir2'
_chemical_formula_weight         880.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.987(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4627(9)
_cell_length_b                   18.1472(12)
_cell_length_c                   12.9349(9)
_cell_measurement_reflns_used    9790
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.48
_cell_measurement_theta_min      2.24
_cell_volume                     2918.3(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'BrukerD8 venture microsource'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0887
_diffrn_reflns_av_unetI/netI     0.0662
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            25605
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.550
_diffrn_reflns_theta_min         2.245
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.490
_exptl_absorpt_correction_T_max  0.3962
_exptl_absorpt_correction_T_min  0.2203
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1673 before and 0.0924 after correction. The Ratio of minimum to maximum transmission is 0.2110. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.005
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.19
_refine_diff_density_max         3.067
_refine_diff_density_min         -2.772
_refine_diff_density_rms         0.326
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.280
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     336
_refine_ls_number_reflns         6705
_refine_ls_number_restraints     190
_refine_ls_restrained_S_all      1.266
_refine_ls_R_factor_all          0.1176
_refine_ls_R_factor_gt           0.1097
_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^)+(0.0001P)^2^+179.8159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2322
_refine_ls_wR_factor_ref         0.2356
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6058
_reflns_number_total             6705
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02109_si_005.cif
_cod_data_source_block           cxy0997_0m
_cod_depositor_comments
;Adding full bibliography for 4517774--4517778.cif.

 Adding full bibliography for 4517774--4517778.cif.
;
_cod_database_code               4517775
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.266
_shelx_estimated_absorpt_t_min   0.157
_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
2. Restrained distances
 Ir1A-C18A = Ir1A-C17A = Ir1A-C16A = Ir1A-C14A = Ir1A-C15A
 2.14 with sigma of 0.02
 C23A-C14 = C23-C14A
 1.5 with sigma of 0.02
 C25A-C23A = C24A-C23A = C24-C23 = C25-C23 = C26-C23 = C26A-C23A
 1.54 with sigma of 0.02
 C18A-C15A
 2.31 with sigma of 0.04
 C23-C15 = C23A-C15A
 2.59 with sigma of 0.04
 C24A-C26A = C26-C24
 2.52 with sigma of 0.04
 C14-C25 = C14-C24 = C14-C26
 2.5 with sigma of 0.04
 C14A-C26A = C14A-C25A = C14A-C24A
 2.5 with sigma of 0.04
 C25-C24 = C24A-C25A
 2.52 with sigma of 0.04
 C26A-C25A = C26-C25
 2.52 with sigma of 0.04
 C18A-C17A \\sim C18-C17 \\sim C17-C16 \\sim C17A-C16A \\sim C16A-C15A \\sim
C16-C15 \\sim C15-C14 ~
 C15A-C14A \\sim C18-C14 \\sim C18A-C14A
 with sigma of 0.02
3. Restrained planarity
 C17, C18, C14, C16, C15
 with sigma of 0.1
 C15A, C16A, C17A, C18A, C14A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C21 \\sim C19 \\sim C20 \\sim C22 \\sim C17 \\sim C16 \\sim C15 \\sim C14 \\sim
C18 \\sim C23A \\sim C25A \\sim C24A \\sim C26A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Ir1) = Uanis(Ir1A)
Uanis(C18) = Uanis(C18A)
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C17) = Uanis(C17A)
Uanis(Cl4A) = Uanis(Cl4)
Uanis(C23) = Uanis(C23A)
Uanis(C24) = Uanis(C24A)
Uanis(C26) = Uanis(C26A)
Uanis(C14) = Uanis(C14A)
Uanis(C25) = Uanis(C25A)
5. Others
 Sof(Cl4A)=Sof(Ir1A)=Sof(C18A)=Sof(H18A)=Sof(C14A)=Sof(C15A)=Sof(H15A)=
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(C23A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C26A)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(Ir1)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C14)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C16)=Sof(H16)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C15)=Sof(H15)=Sof(C23)=Sof(Cl4)=FVAR(1)
6.a Everything fixed:
 H25A, H25B, H25C, H25D, H25E, H25F
6.b Me refined as rotating group:
 C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C24A(H24D,H24E,H24F), C26A(H26D,
 H26E,H26F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C3(H3), C18(H18), C16(H16), C15(H15), C18A(H18A), C15A(H15A),
 C16A(H16A)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C8(H8A,H8B,H8C),
 C11(H11A,H11B,H11C), C9(H9A,H9B,H9C), C22(H22A,H22B,H22C), C12(H12A,H12B,H12C),
  C13(H13A,H13B,H13C)
;
_olex2_submission_special_instructions 'No special instructions were received'