A cascade deprotonation/intramolecular aldol reaction of α-carbonyl sulfonium ylides with 2-mercaptoindole-3-carbaldehydes and 2-mercaptobenzaldehydes to access thieno[2,3-<i>b</i>]indoles and benzothiophenes.
Yang, Lei; Zhou, Shun; Zhao, Jian-Qiang; You, Yong; Wang, Zhen-Hua; Zhou, Ming-Qiang; Yuan, Wei-Cheng; Organic & biomolecular chemistry 19 (2021) 3678–3686; doi:10.1039/d1ob00349f

data_7157987
_publ_section_title
;
 A cascade deprotonation/intramolecular aldol reaction of \a-carbonyl
 sulfonium ylides with 2-mercaptoindole-3-carbaldehydes and
 2-mercaptobenzaldehydes to access thieno[2,3-<i>b</i>]indoles and
 benzothiophenes.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3678
_journal_page_last               3686
_journal_paper_doi               10.1039/d1ob00349f
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C22 H18 Br N O3 S'
_chemical_formula_sum            'C22 H18 Br N O3 S'
_chemical_formula_weight         456.34
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-01-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-08 deposited with the CCDC.	2021-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                88.986(9)
_cell_angle_beta                 65.263(11)
_cell_angle_gamma                80.064(9)
_cell_formula_units_Z            2
_cell_length_a                   9.6907(12)
_cell_length_b                   10.3979(10)
_cell_length_c                   11.4082(13)
_cell_measurement_reflns_used    2600
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6980
_cell_measurement_theta_min      4.2490
_cell_volume                     1026.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -56.00  37.00   1.00    1.00    --  -33.50  37.00  90.00   93
  2  \w   -104.00 -11.00   1.00    1.00    --  -33.50 -37.00 -90.00   93
  3  \w   -108.00 -32.00   1.00    1.00    --  -33.50 178.00 -60.00   76
  4  \w     57.00 110.00   1.00    1.00    --   36.47 178.00 -90.00   53
  5  \w     57.00 110.00   1.00    1.00    --   36.47 178.00   0.00   53
  6  \w    -33.00  65.00   1.00    1.00    --   36.47 -77.00-150.00   98
  7  \w     18.00 105.00   1.00    1.00    --   36.47  57.00   0.00   87
  8  \w    -36.00  74.00   1.00    1.00    --   36.47 -19.00  30.00  110
  9  \w     -4.00  77.00   1.00    1.00    --   36.47 -99.00 -30.00   81
 10  \w     46.00  77.00   1.00    1.00    --   36.47 -99.00  30.00   31
 11  \w     51.00  93.00   1.00    1.00    --   36.47  77.00 150.00   42
 12  \w      9.00  45.00   1.00    1.00    --   36.47  77.00 150.00   36
 13  \w    100.00 137.00   1.00    1.50    --  108.00  45.00-120.00   37
 14  \w     39.00  94.00   1.00    1.50    --  108.00 -94.00 150.00   55
 15  \w     46.00 122.00   1.00    1.50    --  108.00 -30.00  90.00   76
 16  \w    112.00 137.00   1.00    1.50    --  108.00 -77.00 -90.00   25
 17  \w     41.00 124.00   1.00    1.50    --  108.00 -61.00 150.00   83
 18  \w     46.00 122.00   1.00    1.50    --  108.00 -61.00   0.00   76
 19  \w    117.00 146.00   1.00    1.50    --  108.00 111.00-150.00   29
 20  \w     40.00 122.00   1.00    1.50    --  108.00 -61.00 -90.00   82
 21  \w     71.00 112.00   1.00    1.50    --  108.00-111.00 -90.00   41
 22  \w     40.00  66.00   1.00    1.50    --  108.00 -77.00 -90.00   26
 23  \w     79.00 106.00   1.00    1.50    --  108.00-111.00   0.00   27
 24  \w     98.00 178.00   1.00    1.50    --  108.00  45.00  60.00   80
 25  \w    110.00 170.00   1.00    1.50    --  108.00  61.00 -90.00   60
 26  \w     36.00 153.00   1.00    1.50    --  108.00 -15.00-120.00  117
 27  \w     75.00 111.00   1.00    1.50    --  108.00-111.00  90.00   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0376332000
_diffrn_orient_matrix_UB_12      0.1369714000
_diffrn_orient_matrix_UB_13      0.0669332000
_diffrn_orient_matrix_UB_21      0.1067284000
_diffrn_orient_matrix_UB_22      -0.0484901000
_diffrn_orient_matrix_UB_23      0.0669189000
_diffrn_orient_matrix_UB_31      0.1374066000
_diffrn_orient_matrix_UB_32      0.0397779000
_diffrn_orient_matrix_UB_33      -0.1150195000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0231
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7270
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.099
_diffrn_reflns_theta_max         67.099
_diffrn_reflns_theta_min         4.275
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.867
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.476
_exptl_crystal_description       block
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.416
_refine_diff_density_min         -0.535
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3682
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0568P)^2^+0.1797P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1026
_refine_ls_wR_factor_ref         0.1104
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3068
_reflns_number_total             3682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00349f2.cif
_cod_data_source_block           20200109
_cod_depositor_comments          'Adding full bibliography for 7157987.cif.'
_cod_database_code               7157987
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H40O2N1S1Br1
_shelx_estimated_absorpt_t_max   0.698
_shelx_estimated_absorpt_t_min   0.497
_reflns_odcompleteness_completeness 99.84
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C9(H9), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17)
2.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              56498
_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 1.438
_oxdiff_exptl_absorpt_empirical_full_min 0.827