Mechanistic Study of Enantioselective Pd-Catalyzed C(sp3)‒H Activation of Thioethers Involving Two Distinct Stereomodels
Saint-Denis, Tyler G.; Lam, Nelson Y. S.; Chekshin, Nikita; Richardson, Paul F.; Chen, Jason S.; Elleraas, Jeff; Hesp, Kevin D.; Schmitt, Daniel C.; Lian, Yajing; Huh, Chan Woo; Yu, Jin-Quan; ACS Catalysis  (2021) 9738–9753; doi:10.1021/acscatal.1c02808

data_4518906
_publ_section_title
;
 Mechanistic Study of Enantioselective Pd-Catalyzed C(sp3)--H Activation
 of Thioethers Involving Two Distinct Stereomodels
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              9738
_journal_page_last               9753
_journal_paper_doi               10.1021/acscatal.1c02808
_journal_year                    2021
_chemical_formula_moiety         'C64 H96 O8 Pd4 S4'
_chemical_formula_sum            'C64 H96 O8 Pd4 S4'
_chemical_formula_weight         1547.24
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-27
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                95.3590(10)
_cell_angle_beta                 97.3220(10)
_cell_angle_gamma                110.0590(10)
_cell_formula_units_Z            1
_cell_length_a                   10.4226(5)
_cell_length_b                   10.7688(6)
_cell_length_c                   16.5741(9)
_cell_measurement_reflns_used    9808
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.39
_cell_measurement_theta_min      2.23
_cell_volume                     1714.30(16)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2017)'
_computing_data_collection       'APEX3 v2017.3-0 (Bruker, 2017)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 8.258
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            32116
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.369
_diffrn_reflns_theta_min         1.252
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.203
_exptl_absorpt_correction_T_max  0.4910
_exptl_absorpt_correction_T_min  0.4554
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0749 before and 0.0361 after correction. The Ratio of minimum to maximum transmission is 0.9277. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.175
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.248
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         7001
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0250
_refine_ls_R_factor_gt           0.0216
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0272P)^2^+1.7451P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0541
_refine_ls_wR_factor_ref         0.0567
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6399
_reflns_number_total             7001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02808_si_005.cif
_cod_data_source_block           yu130
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        1714.29(16)
_cod_database_code               4518906
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.817
_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. Uiso/Uaniso restraints and constraints
Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of
0.003 and sigma for terminal atoms of 0.006
3.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C10(H10), C20(H20), C22(H22), C24(H24)
3.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              25802
_shelx_hkl_checksum              47004
_olex2_submission_special_instructions 'No special instructions were received'