Catalytic asymmetric functionalization and dearomatization of thiophenes.
Zhao, Zhengxing; Li, Yingxin; Jia, Shiqi; Peng, Lei; Zhang, Zian; Wu, Fengdi; Wang, Pengfei; Qin, Wenling; Lan, Yu; Yan, Hailong; Chemical science 15 (2024) 14295–14303; doi:10.1039/d4sc03530e

data_1572240
_publ_section_title
;
 Catalytic asymmetric functionalization and dearomatization of thiophenes.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14295
_journal_page_last               14303
_journal_paper_doi               10.1039/d4sc03530e
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H13 Br O S'
_chemical_formula_sum            'C22 H13 Br O S'
_chemical_formula_weight         405.29
_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             2022-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2022-08-23 deposited with the CCDC.	2024-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.132(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0211(4)
_cell_length_b                   8.9321(3)
_cell_length_c                   11.4528(6)
_cell_measurement_reflns_used    6955
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.9720
_cell_measurement_theta_min      1.9200
_cell_volume                     848.64(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0892
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.906
_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     47.00  87.00   1.00    3.29    --   18.89 178.00   0.00   40
  2  \w      5.00  31.00   1.00    3.29    --   18.89  77.00  60.00   26
  3  \w    -52.00  74.00   1.00    3.29    --   18.89   0.00  90.00  126
  4  \w    -27.00  -1.00   1.00    3.29    --  -18.78  19.00-150.00   26
  5  \w     39.00  64.00   1.00    3.29    --   18.58 178.00  30.00   25
  6  \w    -30.00  18.00   1.00    3.29    --   18.58 -57.00  60.00   48
  7  \w     15.00  62.00   1.00    3.29    --   18.58-109.00 178.00   47
  8  \w      8.00  54.00   1.00    3.29    --  -18.78   0.00 -90.00   46
  9  \w    -37.00  50.00   1.00    3.29    --  -18.78  57.00   0.00   87
 10  \w    -42.00  11.00   1.00    3.29    --  -18.78 -77.00 -60.00   53
 11  \w    -88.00   3.00   1.00    3.29    --  -18.78 -57.00  90.00   91
 12  \w    -88.00   3.00   1.00    3.29    --  -18.78 -57.00-150.00   91
 13  \w    -74.00 -42.00   1.00    3.29    --  -18.78 121.00  13.74   32
 14  \w    -81.00 -44.00   1.00    3.29    --  -18.78 132.00-156.47   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0307967000
_diffrn_orient_matrix_UB_12      0.0214887000
_diffrn_orient_matrix_UB_13      0.0457706000
_diffrn_orient_matrix_UB_21      0.0616022000
_diffrn_orient_matrix_UB_22      -0.0418567000
_diffrn_orient_matrix_UB_23      0.0469792000
_diffrn_orient_matrix_UB_31      0.0506574000
_diffrn_orient_matrix_UB_32      0.0639646000
_diffrn_orient_matrix_UB_33      0.0153448000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.906
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13415
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.868
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.340
_diffrn_reflns_theta_min         1.934
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.551
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70232
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.586
_exptl_crystal_description       block
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.39
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.299
_refine_diff_density_min         -0.818
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Flack x determined using 1448 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         4043
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0347
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0419P)^2^+0.0955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.825
_reflns_number_gt                3564
_reflns_number_total             4043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03530e2.cif
_cod_data_source_block           20220613-zzx-1290
_cod_depositor_comments
'Adding full bibliography for 1572238--1572242.cif.'
_cod_original_cell_volume        848.64(7)
_cod_database_code               1572240
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H13 Br O S'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C6(H6), C19(H19), C20(H20), C9(H9), C2(H2), C12(H12), C18(H18),
 C7(H7), C10(H10), C1(H1), C11(H11)
;
_shelx_res_checksum              79815
_shelx_hkl_checksum              89802
_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 1.274
_oxdiff_exptl_absorpt_empirical_full_min 0.766