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_1566426
_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_formula_moiety         'C20 H17 S, C F3 O3 S'
_chemical_formula_sum            'C21 H17 F3 O3 S2'
_chemical_formula_weight         438.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-12-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-12-20 deposited with the CCDC.	2022-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.659(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8793(2)
_cell_length_b                   13.4651(3)
_cell_length_c                   16.2393(3)
_cell_measurement_reflns_used    9576
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.6660
_cell_measurement_theta_min      4.2510
_cell_volume                     1935.17(7)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(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 0.982
_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    -64.00  27.00   1.00    1.00    --  -40.73  38.00 -30.00   91
  2  \w     15.00  65.00   1.00    1.00    --   40.73 -99.00   0.00   50
  3  \w     25.00 109.00   1.00    1.00    --  107.58 -95.00 120.00   84
  4  \w     81.00 129.00   1.00    1.00    --  107.58 -45.00  60.00   48
  5  \w     62.00 109.00   1.00    1.00    --  107.58-125.00 -30.00   47
  6  \w     96.00 122.00   1.00    1.00    --  107.58-125.00-150.00   26
  7  \w     99.00 132.00   1.00    1.00    --  107.58 -45.00 -90.00   33
  8  \w     79.00 177.00   1.00    1.00    --  107.58  30.00-120.00   98
  9  \w    111.00 172.00   1.00    1.00    --  107.58 125.00-180.00   61
 10  \w     93.00 146.00   1.00    1.00    --  107.58  45.00 -60.00   53
 11  \w     95.00 138.00   1.00    1.00    --  107.58 125.00  60.00   43
 12  \w     82.00 178.00   1.00    1.00    --  107.58  45.00 150.00   96
 13  \w     56.00 135.00   1.00    1.00    --  107.58 -61.00 150.00   79
 14  \w     51.00 109.00   1.00    1.00    --  107.58 -95.00   0.00   58
 15  \w     41.00  88.00   1.00    1.00    --  107.58 -45.00 -90.00   47
 16  \w     38.00  95.00   1.00    1.00    --   40.73-125.00-150.00   57
 17  \w   -110.00 -23.00   1.00    1.00    --  -40.73 -57.00  60.00   87
 18  \w   -114.00 -17.00   1.00    1.00    --  -40.73 -38.00 150.00   97
;
_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      -0.0145607000
_diffrn_orient_matrix_UB_12      -0.0979410000
_diffrn_orient_matrix_UB_13      -0.0490595000
_diffrn_orient_matrix_UB_21      0.1185441000
_diffrn_orient_matrix_UB_22      -0.0483783000
_diffrn_orient_matrix_UB_23      0.0620439000
_diffrn_orient_matrix_UB_31      -0.1264842000
_diffrn_orient_matrix_UB_32      -0.0339547000
_diffrn_orient_matrix_UB_33      0.0530901000
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12756
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.982
_diffrn_reflns_theta_min         4.271
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.944
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71073
_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    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.603
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.083
_refine_ls_extinction_coef       0.0127(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         3845
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0674P)^2^+1.1454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1181
_refine_ls_wR_factor_ref         0.1194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3684
_reflns_number_total             3845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00341d2.cif
_cod_data_source_block           zqc-s
_cod_database_code               1566426
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 F1B-C20 \\sim F2-C20
 with sigma of 0.02
 F3-C20 \\sim F2B-C20
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F2, F2B, F4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F1B, F3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(F1B)=Sof(F3)=1-FVAR(1)
 Sof(F2)=Sof(F2B)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C16(H16), C17(H17),
 C18(H18), C19(H19), C21(H21)
5.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              59442
_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 1.376
_oxdiff_exptl_absorpt_empirical_full_min 0.745