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_1572239
_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         'C20 H11 Br O S2'
_chemical_formula_sum            'C20 H11 Br O S2'
_chemical_formula_weight         411.32
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-11
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   12.4762(8)
_cell_length_b                   12.4762(8)
_cell_length_c                   9.5066(6)
_cell_measurement_reflns_used    2425
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      25.6070
_cell_measurement_theta_min      1.8750
_cell_volume                     1281.51(14)
_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_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_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 0.857
_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    -77.00  38.00   1.00    3.31    --  -18.93   0.00 -90.00  115
  2  \w    -77.00  38.00   1.00    3.31    --  -18.93   0.00  90.00  115
;
_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      -0.0168420000
_diffrn_orient_matrix_UB_12      0.0340784000
_diffrn_orient_matrix_UB_13      -0.0455467000
_diffrn_orient_matrix_UB_21      0.0178319000
_diffrn_orient_matrix_UB_22      0.0465915000
_diffrn_orient_matrix_UB_23      0.0520675000
_diffrn_orient_matrix_UB_31      0.0609390000
_diffrn_orient_matrix_UB_32      0.0311614000
_diffrn_orient_matrix_UB_33      -0.0280109000
_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  0.0325
_diffrn_reflns_av_unetI/netI     0.0753
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6071
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.853
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.016
_diffrn_reflns_theta_min         1.885
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.653
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76635
_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    1.599
_exptl_crystal_description       block
_exptl_crystal_F_000             618
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.623
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 1066 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3885
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0192P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0656
_refine_ls_wR_factor_ref         0.0774
_reflns_Friedel_coverage         0.990
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.849
_reflns_number_gt                2971
_reflns_number_total             3885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03530e2.cif
_cod_data_source_block           20220411-zzx-0411-200k
_cod_depositor_comments
'Adding full bibliography for 1572238--1572242.cif.'
_cod_original_cell_volume        1281.50(18)
_cod_database_code               1572239
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H11 Br O S2'
_shelx_estimated_absorpt_t_max   0.484
_shelx_estimated_absorpt_t_min   0.448
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C19(H19), C16(H16), C14(H14), C8(H8), C18(H18), C4(H4), C17(H17),
 C7(H7), C3(H3)
2.b Tetrahedral OH refined with riding coordinates:
 O1(H1)
;
_shelx_res_checksum              50191
_shelx_hkl_checksum              59765
_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 1.127
_oxdiff_exptl_absorpt_empirical_full_min 0.857