Probing Catalyst Speciation in Pd-MPAAM-Catalyzed Enantioselective C(sp3)‒H Arylation: Catalyst Improvement via Destabilization of Off-Cycle Species
Hao, Wei; Bay, Katherine L.; Harris, Caleb F.; King, Daniel S.; Guzei, Ilia A.; Aristov, Michael M.; Zhuang, Zhe; Plata, R. Erik; Hill, David E.; Houk, K. N.; Berry, John F.; Yu, Jin-Quan; Blackmond, Donna G.; ACS Catalysis  (2021) 11040–11048; doi:10.1021/acscatal.1c02805

data_4518968
_publ_section_title
;
 Probing Catalyst Speciation in Pd-MPAAM-Catalyzed Enantioselective
 C(sp3)--H Arylation: Catalyst Improvement via Destabilization of
 Off-Cycle Species
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              11040
_journal_page_last               11048
_journal_paper_doi               10.1021/acscatal.1c02805
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C24 H32 N2 O2 Pd S2'
_chemical_formula_sum            'C24 H32 N2 O2 Pd S2'
_chemical_formula_weight         551.03
_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     dual
_audit_creation_date             2018-09-11
_audit_creation_method
;
Olex2 1.2-beta
(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                   11.017(5)
_cell_length_b                   14.127(4)
_cell_length_c                   16.002(6)
_cell_measurement_reflns_used    8517
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.922
_cell_measurement_theta_min      2.244
_cell_volume                     2490.5(16)
_computing_cell_refinement       'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_collection       'APEX3 Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_reduction        'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.02
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_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  0.0573
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            38356
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.493
_diffrn_reflns_theta_min         1.923
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.935
_exptl_absorpt_correction_T_max  0.9094
_exptl_absorpt_correction_T_min  0.8603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1071 before and 0.0551 after correction. The Ratio of minimum to maximum transmission is 0.9460. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.344
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 2251 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.018(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     279
_refine_ls_number_reflns         5717
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0252
_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^)+(0.0202P)^2^+0.9949P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0501
_refine_ls_wR_factor_ref         0.0513
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5340
_reflns_number_total             5717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02805_si_003.cif
_cod_data_source_block           berry864
_cod_original_cell_volume        2490.4(15)
_cod_database_code               4518968
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.900
_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,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Same fragment restrains
{C19, C20, C21, C22, C23, C24} sigma for 1-2: 0.02, 1-3: 0.04
{C19A, C20A, C21A, C22A, C23A, C24A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C6, C7, C8, C9, C10, C11}
3. Others
 Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(C24A)=Sof(H24A)=Sof(C23A)=Sof(H23A)=
 Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=1-FVAR(1)
 Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=
 Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C3(H3), C15(H15)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C14(H14A,H14B), C18(H18A,H18B), C18(H18C,H18D)
4.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24), C24A(H24A), C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A)
4.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C17(H17A,H17B,H17C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              84670
_shelx_hkl_checksum              90571
_olex2_submission_special_instructions 'No special instructions were received'