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_1572241
_publ_section_title
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 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         'C21 H12 Br2 O3 S2'
_chemical_formula_sum            'C21 H12 Br2 O3 S2'
_chemical_formula_weight         536.24
_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             2022-07-09
_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                 109.024(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1561(6)
_cell_length_b                   10.0689(3)
_cell_length_c                   15.4836(7)
_cell_measurement_reflns_used    6105
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.5900
_cell_measurement_theta_min      1.7680
_cell_volume                     1939.05(15)
_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 0.890
_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     -9.00  39.00   1.00   11.50    --   18.74  77.00  30.00   48
  2  \w     -1.00  27.00   1.00   11.50    --   18.74  90.00  84.00   28
  3  \w     48.00  94.00   1.00   11.50    --   18.74 178.00   0.00   46
  4  \w    -50.00 -11.00   1.00   11.50    --   18.74 -57.00  30.00   39
  5  \w     -1.00  88.00   1.00   11.50    --   18.74  57.00-180.00   89
  6  \w    -13.00  24.00   1.00   11.50    --  -18.93  56.00 -22.00   37
  7  \w    -90.00  22.00   1.00   11.50    --  -18.93 -19.00   0.00  112
;
_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      0.0307072000
_diffrn_orient_matrix_UB_12      -0.0571302000
_diffrn_orient_matrix_UB_13      -0.0020027000
_diffrn_orient_matrix_UB_21      -0.0458427000
_diffrn_orient_matrix_UB_22      -0.0291441000
_diffrn_orient_matrix_UB_23      -0.0322737000
_diffrn_orient_matrix_UB_31      0.0143665000
_diffrn_orient_matrix_UB_32      0.0291716000
_diffrn_orient_matrix_UB_33      -0.0360837000
_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  0.0314
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.890
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15893
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.087
_diffrn_reflns_theta_min         1.637
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.417
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51516
_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    1.837
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.392
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 2333 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.002(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         8839
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0204P)^2^+0.2777P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0608
_refine_ls_wR_factor_ref         0.0734
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.806
_reflns_number_gt                6533
_reflns_number_total             8839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03530e2.cif
_cod_data_source_block           20220708-zzx-1312
_cod_depositor_comments
;
Adding full bibliography for 1572238--1572242.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C42 H24 Br4 O6 S4'
_cod_original_formula_weight         1072.49
_cod_original_formula_moiety         '2(C21 H12 Br2 O3 S2)'
_cod_original_formula_units_Z            2
_cod_database_code               1572241
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N'
_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:
 C00Q(H00Q), C00T(H00T), C00U(H00U), C012(H012), C013(H013), C014(H014),
 C015(H015), C016(H016), C017(H017), C019(H019), C01B(H01B), C01C(H01C),
 C01E(H01L), C01F(H01M), C01G(H01G), C01H(H01H), C01I(H01N), C01J(H01J)
2.b Idealised Me refined as rotating group:
 C01A(H01F,H01I,H01K), C01K(H01A,H01D,H01E)
;
_shelx_res_checksum              25520
_shelx_hkl_checksum              43909
_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 1.321
_oxdiff_exptl_absorpt_empirical_full_min 0.691