Regioselective Reversal Cyclization To Access either Eight-Membered Sulfur-Containing Heterocycle-Fused γ-Pyrones or 2-(1,4-Dithianyl)-4-pyrones from the Same Precursors.
Tang, Ling; Yang, Qin; Zhang, Jianfang; Deng, Guisheng; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03303

data_4037840
_publ_section_title
;
 Regioselective Reversal Cyclization To Access either Eight-Membered
 Sulfur-Containing Heterocycle-Fused \g-Pyrones or
 2-(1,4-Dithianyl)-4-pyrones from the Same Precursors.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03303
_journal_year                    2020
_chemical_formula_moiety         'C26 H22 O4 S2'
_chemical_formula_sum            'C26 H22 O4 S2'
_chemical_formula_weight         462.55
_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     dual
_audit_creation_date             2018-08-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                96.684(6)
_cell_angle_beta                 91.881(7)
_cell_angle_gamma                101.786(7)
_cell_formula_units_Z            2
_cell_length_a                   7.8723(7)
_cell_length_b                   11.7079(8)
_cell_length_c                   12.5625(9)
_cell_measurement_reflns_used    5183
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.5730
_cell_measurement_theta_min      4.9620
_cell_volume                     1123.84(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_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    -29.00  31.00   1.00    5.00    --  -34.73  57.00-120.00   60
  2  \w     22.00  52.00   1.00    5.00    --   34.73  57.00 -30.00   30
  3  \w     26.00  94.00   1.00    5.00    --   34.73  38.00   0.00   68
  4  \w     73.00 102.00   1.00    5.00    --   34.73  77.00  90.00   29
  5  \w     51.00  90.00   1.00    5.00    --   34.73  19.00 120.00   39
  6  \w     21.00  95.00   1.00    5.00    --   34.73  57.00  30.00   74
  7  \w    119.00 172.00   1.00   20.00    --  105.88  77.00 -60.00   53
  8  \w    137.00 168.00   1.00   20.00    --  105.88  61.00 -90.00   31
  9  \w    127.00 173.00   1.00   20.00    --  105.88  77.00-150.00   46
 10  \w    125.00 158.00   1.00   20.00    --  105.88  77.00-180.00   33
 11  \w    117.00 173.00   1.00   20.00    --  105.88  77.00-120.00   56
 12  \w    126.00 158.00   1.00   20.00    --  105.88  77.00 -30.00   32
 13  \w    123.00 159.00   1.00   20.00    --  105.88  77.00  60.00   36
 14  \w    125.00 173.00   1.00   20.00    --  105.88  77.00 120.00   48
 15  \w    122.00 171.00   1.00   20.00    --  105.88  77.00 150.00   49
 16  \w    118.00 170.00   1.00   20.00    --  105.88  77.00  90.00   52
 17  \w     85.00 111.00   1.00   20.00    --  105.88  30.00   0.00   26
 18  \w     89.00 121.00   1.00   20.00    --  105.88  56.00  -4.00   32
 19  \w     89.00 130.00   1.00   20.00    --  105.88  61.00 -60.00   41
 20  \w     89.00 167.00   1.00   20.00    --  105.88  61.00   0.00   78
 21  \w     88.00 114.00   1.00   20.00    --  105.88  61.00  30.00   26
 22  \w     80.00 105.00   1.00   20.00    --  105.88  77.00 -30.00   25
 23  \w     80.00 106.00   1.00   20.00    --  105.88  77.00 -60.00   26
 24  \w     88.00 115.00   1.00   20.00    --  105.88  61.00 -90.00   27
 25  \w     84.00 114.00   1.00   20.00    --  105.88  30.00 -90.00   30
 26  \w     85.00 113.00   1.00   20.00    --  105.88  30.00-150.00   28
 27  \w     89.00 114.00   1.00   20.00    --  105.88  61.00-150.00   25
 28  \w     84.00 113.00   1.00   20.00    --  105.88  30.00-180.00   29
 29  \w     79.00 106.00   1.00   20.00    --  105.88  77.00-180.00   27
 30  \w     80.00 105.00   1.00   20.00    --  105.88  77.00-150.00   25
 31  \w     79.00 105.00   1.00   20.00    --  105.88  77.00-120.00   26
 32  \w     82.00 109.00   1.00   20.00    --  105.88  77.00 -90.00   27
 33  \w     84.00 110.00   1.00   20.00    --  105.88  30.00 -30.00   26
 34  \w     84.00 111.00   1.00   20.00    --  105.88  30.00 -60.00   27
 35  \w     85.00 132.00   1.00   20.00    --  105.88  30.00-120.00   47
 36  \w     79.00 106.00   1.00   20.00    --  105.88  77.00   0.00   27
 37  \w     79.00 165.00   1.00   20.00    --  105.88  77.00  30.00   86
 38  \w     88.00 114.00   1.00   20.00    --  105.88  61.00 120.00   26
 39  \w     79.00 105.00   1.00   20.00    --  105.88  77.00 150.00   26
 40  \w     79.00 108.00   1.00   20.00    --  105.88  77.00 120.00   29
 41  \w     79.00 105.00   1.00   20.00    --  105.88  77.00  90.00   26
 42  \w     80.00 106.00   1.00   20.00    --  105.88  77.00  60.00   26
 43  \w     85.00 112.00   1.00   20.00    --  105.88  30.00  90.00   27
 44  \w     85.00 112.00   1.00   20.00    --  105.88  30.00 120.00   27
 45  \w     85.00 112.00   1.00   20.00    --  105.88  30.00 150.00   27
 46  \w     37.00 107.00   1.00   20.00    --  105.88 -94.00 150.00   70
 47  \w     56.00 114.00   1.00   20.00    --  105.88-111.00  30.00   58
 48  \w     38.00  78.00   1.00    5.00    --   34.73-125.00  90.00   40
 49  \w     38.00 103.00   1.00   20.00    --  105.88 -94.00  60.00   65
 50  \w     37.00  94.00   1.00   20.00    --  105.88 -94.00 -60.00   57
 51  \w     37.00  68.00   1.00   20.00    --  105.88 -94.00-150.00   31
 52  \w     37.00  98.00   1.00   20.00    --  105.88 -94.00-120.00   61
 53  \w     53.00  86.00   1.00    5.00    --   34.73-125.00-180.00   33
 54  \w      4.00  74.00   1.00    5.00    --   34.73 -99.00 -60.00   70
 55  \w    -11.00  48.00   1.00    5.00    --   34.73 -57.00   0.00   59
 56  \w     19.00 102.00   1.00    5.00    --   34.73  38.00-150.00   83
 57  \w     69.00  96.00   1.00    5.00    --   34.73  77.00-120.00   27
 58  \w     64.00 101.00   1.00    5.00    --   34.73  57.00-120.00   37
 59  \w     34.00  61.00   1.00    5.00    --   34.73  57.00-120.00   27
 60  \w      9.00  40.00   1.00    5.00    --   34.73  77.00 -30.00   31
 61  \w     12.00  39.00   1.00    5.00    --   34.73  77.00  30.00   27
 62  \w      9.00  69.00   1.00    5.00    --   34.73  77.00  90.00   60
 63  \w      9.00  63.00   1.00    5.00    --   34.73  77.00 150.00   54
 64  \w    -33.00  51.00   1.00    5.00    --   34.73 -57.00  90.00   84
 65  \w    -29.00  25.00   1.00    5.00    --   34.73 -77.00 -30.00   54
 66  \w    -30.00  46.00   1.00    5.00    --   34.73 -57.00-180.00   76
 67  \w      9.00  66.00   1.00    5.00    --   34.73  77.00-120.00   57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1897149000
_diffrn_orient_matrix_UB_12      -0.0677286000
_diffrn_orient_matrix_UB_13      -0.0218685000
_diffrn_orient_matrix_UB_21      0.0294474000
_diffrn_orient_matrix_UB_22      -0.0831796000
_diffrn_orient_matrix_UB_23      0.0819984000
_diffrn_orient_matrix_UB_31      -0.0569273000
_diffrn_orient_matrix_UB_32      0.0827799000
_diffrn_orient_matrix_UB_33      0.0899721000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0620
_diffrn_reflns_av_unetI/netI     0.0725
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13781
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         3.888
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.404
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             484
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.313
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         3961
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.151
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0550
_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^)+(0.0927P)^2^+0.0413P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1658
_refine_ls_wR_factor_ref         0.1788
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3079
_reflns_number_total             3961
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03303_si_001.cif
_cod_data_source_block           exp_496
_cod_original_cell_volume        1123.83(15)
_cod_database_code               4037840
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C80 H40 O4 S2 '
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C16(H16A,H16B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C19(H19), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_olex2_date_sample_data_collection 2018-08-15
_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 2.655
_oxdiff_exptl_absorpt_empirical_full_min 0.372