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_4517776
_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_absolute_configuration ad
_chemical_formula_moiety         'C23 H17 F6 N O4 S'
_chemical_formula_sum            'C23 H17 F6 N O4 S'
_chemical_formula_weight         517.43
_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   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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.5584(14)
_cell_length_b                   14.559(4)
_cell_length_c                   27.412(7)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.23
_cell_measurement_theta_min      2.63
_cell_volume                     2218.3(10)
_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 0.996
_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  0.1056
_diffrn_reflns_av_unetI/netI     0.0671
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            21556
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        24.702
_diffrn_reflns_theta_max         24.702
_diffrn_reflns_theta_min         2.632
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.228
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.2344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1801 before and 0.1262 after correction. The Ratio of minimum to maximum transmission is 0.3147. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 1147 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(18)
_refine_ls_extinction_coef       0.012(3)
_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   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         3772
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0663
_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^)+(0.1099P)^2^+1.5704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1691
_refine_ls_wR_factor_ref         0.1800
_reflns_Friedel_coverage         0.704
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3225
_reflns_number_total             3772
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02109_si_006.cif
_cod_data_source_block           cxy0994_0m
_cod_depositor_comments
;Adding full bibliography for 4517774--4517778.cif.

 Adding full bibliography for 4517774--4517778.cif.
;
_cod_database_code               4517776
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.933
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 F1-C13 \\sim F1A-C13A
 with sigma of 0.02
 F2-C13 \\sim F2A-C13A
 with sigma of 0.02
 F3-C13 \\sim F3A-C13A
 with sigma of 0.02
 O3-C13 \\sim O3A-C13A
 with sigma of 0.02
 O3-C12 \\sim O3A-C12
 with sigma of 0.02
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 F1-F3 \\sim F1A-F3A
 with sigma of 0.04
 F1-O3 \\sim F1A-O3A
 with sigma of 0.04
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-O3 \\sim F2A-O3A
 with sigma of 0.04
 F3-O3 \\sim F3A-O3A
 with sigma of 0.04
 C13-C12 \\sim C13A-C12
 with sigma of 0.04
 F4-C21 \\sim F4A-C21A
 with sigma of 0.02
 F5-C21 \\sim F5A-C21A
 with sigma of 0.02
 F6-C21 \\sim F6A-C21A
 with sigma of 0.02
 O4-C21 \\sim O4A-C21A
 with sigma of 0.02
 O4-C20 \\sim O4A-C20
 with sigma of 0.02
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F4-O4 \\sim F4A-O4A
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F5-O4 \\sim F5A-O4A
 with sigma of 0.04
 F6-O4 \\sim F6A-O4A
 with sigma of 0.04
 C21-C20 \\sim C21A-C20
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F6A) \\sim Ueq, Uanis(F4A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O4A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C13) = Uanis(C13A)
Uanis(F1A) = Uanis(F1)
Uanis(F3A) = Uanis(F3)
Uanis(F2) = Uanis(F2A)
Uanis(O3) = Uanis(O3A)
Uanis(O4A) = Uanis(O4)
Uanis(C21A) = Uanis(C21)
Uanis(F4A) = Uanis(F4)
Uanis(F5A) = Uanis(F5)
Uanis(F6) = Uanis(F6A)
4. Others
 Sof(O3A)=Sof(C13A)=Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(O3)=Sof(C13)=FVAR(1)
 Sof(F5A)=Sof(F6A)=Sof(C21A)=Sof(F4A)=Sof(O4A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(O4)=Sof(C21)=FVAR(2)
5.a Riding coordinates:
 N1(H1)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C1(H1A,H1B)
5.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C6(H6), C11(H11), C7(H7), C23(H23), C22(H22), C14(H14), C8(H8),
 C9(H9), C10(H10), C15(H15), C19(H19)
;
_olex2_submission_special_instructions 'No special instructions were received'