One-Pot Synthesis of 2,4-Diacyl Thiophenes from α-Oxo Ketene Dithioacetals and Propargylic Alcohols.
Jian, Xue; Bai, Li-Gang; Zhang, Liang; Zhou, Yue; Lin, Xiao-Long; Mou, Neng-Jie; Xiao, Dong-Rong; Luo, Qun-Li; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01093

data_4038607
_publ_section_title
;
 One-Pot Synthesis of 2,4-Diacyl Thiophenes from \a-Oxo Ketene
 Dithioacetals and Propargylic Alcohols.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01093
_journal_year                    2020
_chemical_formula_moiety         'C21 H19 I O2 S2'
_chemical_formula_sum            'C21 H19 I O2 S2'
_chemical_formula_weight         494.38
_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             2019-10-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                94.342(2)
_cell_angle_beta                 106.336(2)
_cell_angle_gamma                116.570(3)
_cell_formula_units_Z            2
_cell_length_a                   9.1035(3)
_cell_length_b                   9.7637(3)
_cell_length_c                   13.8594(4)
_cell_measurement_reflns_used    12282
_cell_measurement_temperature    295.9(3)
_cell_measurement_theta_max      71.6710
_cell_measurement_theta_min      5.1930
_cell_volume                     1027.74(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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_environment      air
_diffrn_ambient_temperature      295.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 1.000
_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   -105.00 -17.00   1.00    1.00    --  -36.10 -38.00  30.00   88
  2  \w   -104.00  -9.00   1.00    1.00    --  -36.10 -77.00 150.00   95
  3  \w    -55.00  33.00   1.00    1.00    --  -36.10  38.00  30.00   88
  4  \w   -103.00 -19.00   1.00    1.00    --  -36.10 -57.00-120.00   84
  5  \w     24.00  90.00   1.00    1.00    --   36.10-126.00 -60.00   66
  6  \w     24.00  90.00   1.00    1.00    --   36.10-126.00  30.00   66
  7  \w     19.00 103.00   1.00    1.00    --   36.10  57.00 -60.00   84
  8  \w     19.00 103.00   1.00    1.00    --   36.10  57.00-150.00   84
  9  \w     24.00  90.00   1.00    1.00    --   36.10-126.00 150.00   66
 10  \w     38.00 112.00   1.00    1.05    --  107.97-112.00-150.00   74
 11  \w    101.00 178.00   1.00    1.05    --  107.97 112.00 -30.00   77
 12  \w     41.00 126.00   1.00    1.05    --  107.97 -61.00  90.00   85
 13  \w     40.00 125.00   1.00    1.05    --  107.97 -45.00 -60.00   85
 14  \w     39.00 110.00   1.00    1.05    --  107.97 -95.00  60.00   71
 15  \w    101.00 178.00   1.00    1.05    --  107.97 112.00  90.00   77
 16  \w     38.00 129.00   1.00    1.05    --  107.97 -30.00 120.00   91
 17  \w     40.00 125.00   1.00    1.05    --  107.97 -45.00   0.00   85
 18  \w     38.00 112.00   1.00    1.05    --  107.97-112.00  30.00   74
 19  \w     40.00 125.00   1.00    1.05    --  107.97 -45.00-180.00   85
 20  \w     91.00 176.00   1.00    1.05    --  107.97  45.00 150.00   85
 21  \w     39.00 110.00   1.00    1.05    --  107.97 -95.00 -90.00   71
 22  \w     70.00 178.00   1.00    1.05    --  107.97  15.00  90.00  108
 23  \w   -104.00  -9.00   1.00    1.00    --  -36.10 -77.00-150.00   95
 24  \w    -55.00  33.00   1.00    1.00    --  -36.10  38.00-150.00   88
 25  \w    -55.00  33.00   1.00    1.00    --  -36.10  38.00 120.00   88
 26  \w   -104.00  -9.00   1.00    1.00    --  -36.10 -77.00   0.00   95
 27  \w      9.00 104.00   1.00    1.00    --   36.10  77.00  90.00   95
 28  \w    -31.00  53.00   1.00    1.00    --   36.10 -57.00-120.00   84
 29  \w     70.00 178.00   1.00    1.05    --  107.97  15.00 -60.00  108
 30  \w     81.00 176.00   1.00    1.05    --  107.97  77.00   0.00   95
 31  \w     81.00 176.00   1.00    1.05    --  107.97  77.00-150.00   95
 32  \w     91.00 176.00   1.00    1.05    --  107.97  45.00 -60.00   85
 33  \w     81.00 176.00   1.00    1.05    --  107.97  77.00  90.00   95
 34  \w     87.00 178.00   1.00    1.05    --  107.97  30.00   0.00   91
 35  \w     81.00 176.00   1.00    1.05    --  107.97  77.00 150.00   95
 36  \w     90.00 175.00   1.00    1.05    --  107.97  61.00 120.00   85
 37  \w     81.00 176.00   1.00    1.05    --  107.97  77.00  60.00   95
 38  \w     81.00 176.00   1.00    1.05    --  107.97  77.00 -60.00   95
 39  \w     81.00 176.00   1.00    1.05    --  107.97  77.00-120.00   95
 40  \w     87.00 178.00   1.00    1.05    --  107.97  30.00-150.00   91
 41  \w   -107.00  -7.00   1.00    1.00    --  -36.10 -19.00  60.00  100
 42  \w   -105.00 -17.00   1.00    1.00    --  -36.10 -38.00-120.00   88
 43  \w      9.00 104.00   1.00    1.00    --   36.10  77.00 -30.00   95
 44  \w      9.00 104.00   1.00    1.00    --   36.10  77.00 150.00   95
 45  \w     19.00 103.00   1.00    1.00    --   36.10  57.00  90.00   84
 46  \w     24.00  90.00   1.00    1.00    --   36.10-126.00-120.00   66
 47  \w     81.00 137.00   1.00    1.05    --  107.97  77.00-180.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1497512000
_diffrn_orient_matrix_UB_12      -0.1426002000
_diffrn_orient_matrix_UB_13      0.0164198000
_diffrn_orient_matrix_UB_21      -0.0249205000
_diffrn_orient_matrix_UB_22      0.1121795000
_diffrn_orient_matrix_UB_23      0.0698410000
_diffrn_orient_matrix_UB_31      -0.1336489000
_diffrn_orient_matrix_UB_32      0.0043645000
_diffrn_orient_matrix_UB_33      -0.0951460000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0818
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            18080
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.063
_diffrn_reflns_theta_min         3.419
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.235
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25837
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.598
_exptl_crystal_description       block
_exptl_crystal_F_000             492
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.37
_refine_diff_density_max         1.763
_refine_diff_density_min         -3.120
_refine_diff_density_rms         0.190
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3664
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0659
_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^)+(0.1300P)^2^+1.3581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1721
_refine_ls_wR_factor_ref         0.1763
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3450
_reflns_number_total             3664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01093_si_002.cif
_cod_data_source_block           luo-2019-10-28
_cod_original_cell_volume        1027.74(6)
_cod_database_code               4038607
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'C1 H1 O1 S1 I1'
_shelx_estimated_absorpt_t_max   0.077
_shelx_estimated_absorpt_t_min   0.072
_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.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C16(H16), C17(H17), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C)
;
_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 2.614
_oxdiff_exptl_absorpt_empirical_full_min 0.532