Torsional Strain Inversed Chemoselectivity in Pd-Catalyzed Atroposelective Carboxylation Reaction of Dibenzothiophenium
Zhang, Qiu-Chi; Xue, Xiaoping; Hong, Biqiong; Gu, Zhenhua; Chemical Science  (2022) –; doi:10.1039/D2SC00341D

data_1566427
_publ_section_title
;
 Torsional Strain Inversed Chemoselectivity in Pd-Catalyzed
 Atroposelective Carboxylation Reaction of Dibenzothiophenium
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00341D
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H29 N O S'
_chemical_formula_sum            'C30 H29 N O S'
_chemical_formula_weight         451.60
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_audit_update_record
;
2021-12-20 deposited with the CCDC.	2022-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   10.0094(4)
_cell_length_b                   10.0094(4)
_cell_length_c                   42.946(2)
_cell_measurement_reflns_used    9309
_cell_measurement_temperature    219.99(10)
_cell_measurement_theta_max      73.1270
_cell_measurement_theta_min      3.0650
_cell_volume                     3726.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      219.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -115.00 -18.00   1.00    1.00    --  -40.73 -37.00   0.00   97
  2  \w    -87.00  41.00   1.00    1.00    --  -40.73   0.00 120.00  128
  3  \w   -109.00 -83.00   1.00    1.00    --  -40.73 -48.00 -24.00   26
  4  \w     35.00  60.00   1.00    1.00    --   40.73-125.00  90.00   25
  5  \w    102.00 128.00   1.00    1.38    --  107.58 125.00  90.00   26
  6  \w     60.00 122.00   1.00    1.38    --  107.58-125.00-180.00   62
  7  \w     26.00 109.00   1.00    1.38    --  107.58 -94.00-150.00   83
  8  \w     92.00 118.00   1.00    1.38    --  107.58  45.00   0.00   26
  9  \w     35.00 130.00   1.00    1.38    --  107.58 -61.00-150.00   95
 10  \w    138.00 178.00   1.00    1.38    --  107.58  45.00   0.00   40
 11  \w     79.00 119.00   1.00    1.38    --  107.58  30.00-120.00   40
 12  \w     83.00 173.00   1.00    1.38    --  107.58  45.00 -60.00   90
 13  \w     94.00 120.00   1.00    1.38    --  107.58 125.00  30.00   26
 14  \w     32.00 140.00   1.00    1.38    --  107.58 -77.00   0.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0754440000
_diffrn_orient_matrix_UB_12      -0.0283782000
_diffrn_orient_matrix_UB_13      -0.0324378000
_diffrn_orient_matrix_UB_21      -0.1228122000
_diffrn_orient_matrix_UB_22      0.0344253000
_diffrn_orient_matrix_UB_23      0.0131671000
_diffrn_orient_matrix_UB_31      0.1037872000
_diffrn_orient_matrix_UB_32      0.1719221000
_diffrn_orient_matrix_UB_33      -0.0079704000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            19253
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.955
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.314
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59368
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.195
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1764 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4999
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0471
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0472P)^2^+0.8848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1060
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4716
_reflns_number_total             4999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00341d2.cif
_cod_data_source_block           128-14
_cod_original_cell_volume        3726.2(4)
_cod_database_code               1566427
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C13(H13), C18(H18),
 C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
2.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              46533
_olex2_date_sample_data_collection 2021-09-14
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.690
_oxdiff_exptl_absorpt_empirical_full_min 0.597