Thioether-enabled palladium-catalyzed atroposelective C–H olefination for N−C and C−C axial chirality
Li, Yanjun; Liou, Yan-Cheng; Chen, Xinran; Ackermann, Lutz; Chemical Science  (2022) –; doi:10.1039/D2SC00748G

data_1566592
_publ_section_title
;
 Thioether-enabled palladium-catalyzed atroposelective C--H olefination
 for N&#x2212;C and C&#x2212;C axial chirality
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00748G
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H22 O3 S'
_chemical_formula_sum            'C23 H22 O3 S'
_chemical_formula_weight         378.46
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2021-12-06
_audit_creation_method
;
FinalCif V92 by Daniel Kratzert, Freiburg 2021,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2021-12-23 deposited with the CCDC.	2022-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                63.599(2)
_cell_angle_beta                 79.446(2)
_cell_angle_gamma                75.302(2)
_cell_formula_units_Z            2
_cell_length_a                   7.2748(7)
_cell_length_b                   12.2905(9)
_cell_length_c                   12.5063(12)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.709
_cell_measurement_theta_min      2.905
_cell_volume                     965.60(15)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
'Bruker BIS V6.2.15/2021-03-15 && APEX4 2021.4-0'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Ag'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_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  0.0258
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            73464
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.732
_diffrn_reflns_theta_min         2.904
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.188
_exptl_absorpt_correction_T_max  0.7565
_exptl_absorpt_correction_T_min  0.7277
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0708 before and 0.0463 after correction.
The Ratio of minimum to maximum transmission is 0.9619.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.281
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 4698 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         9983
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0259
_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^)+(0.0354P)^2^+0.1943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0651
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                9720
_reflns_number_total             9983
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00748g2.cif
_cod_data_source_block           mo_1524_cg_0m
_cod_database_code               1566592
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C45(H45A,H45B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13),
 C15(H15), C17(H17), C18(H18), C26(H26), C27(H27), C28(H28), C29(H29), C32(H32),
  C33(H33), C34(H34), C35(H35), C38(H38), C40(H40), C41(H41)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_estimated_absorpt_t_min   0.967
_shelx_estimated_absorpt_t_max   0.987
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              63359
_shelx_hkl_checksum              2122