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_1566593
_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         'C20 H20 N2 O S'
_chemical_formula_sum            'C20 H20 N2 O S'
_chemical_formula_weight         336.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-26
_audit_creation_method
;
FinalCif V97 by Daniel Kratzert, Freiburg 2022,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2022-01-26 deposited with the CCDC.	2022-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.142(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0831(4)
_cell_length_b                   6.8389(3)
_cell_length_c                   12.0729(5)
_cell_measurement_reflns_used    9719
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      32.919
_cell_measurement_theta_min      3.042
_cell_volume                     864.48(6)
_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 0.942
_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  0.0157
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            30575
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.459
_diffrn_reflns_theta_min         1.785
_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    0.196
_exptl_absorpt_correction_T_max  0.7466
_exptl_absorpt_correction_T_min  0.7261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0903 before and 0.0370 after correction.
The Ratio of minimum to maximum transmission is 0.9725.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_description       block
_exptl_crystal_F_000             356
_exptl_crystal_recrystallization_method
'Crystallized from a mixture of ethyl acetate, dichloromethane and hexane by fullevaporation.'
_exptl_crystal_size_max          0.413
_exptl_crystal_size_mid          0.198
_exptl_crystal_size_min          0.168
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.183
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 2601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         6087
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0250
_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^)+(0.0481P)^2^+0.0813P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0714
_refine_ls_wR_factor_ref         0.0723
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.853
_reflns_number_gt                5968
_reflns_number_total             6087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00748g2.cif
_cod_data_source_block           mo_1565_cg_0m
_cod_database_code               1566593
_shelx_shelxl_version_number     2018/3
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C12(H12), C13(H13), C15(H15),
 C16(H16), C17(H17), C18(H18)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_estimated_absorpt_t_min   0.924
_shelx_estimated_absorpt_t_max   0.968
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              6327
_shelx_hkl_checksum              11596