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_4037841
_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         'C24 H19 O4 S3'
_chemical_formula_sum            'C24 H19 O4 S3'
_chemical_formula_weight         467.57
_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     direct
_audit_creation_date             2019-03-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.351(3)
_cell_angle_beta                 100.885(3)
_cell_angle_gamma                94.385(3)
_cell_formula_units_Z            2
_cell_length_a                   6.3222(2)
_cell_length_b                   13.4523(4)
_cell_length_c                   16.5443(4)
_cell_measurement_reflns_used    7580
_cell_measurement_temperature    293
_cell_measurement_theta_max      71.6170
_cell_measurement_theta_min      4.8320
_cell_volume                     1339.72(7)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -33.00  -5.00   1.00    1.00    --  -34.73 -19.00 -30.00   28
  2  \w    -31.00  51.00   1.00    1.00    --   34.73 -57.00  30.00   82
  3  \w     47.00  75.00   1.00    1.00    --   34.73-125.00  30.00   28
  4  \w     53.00  88.00   1.00    1.00    --   34.73-125.00 -90.00   35
  5  \w     62.00 114.00   1.00    4.00    --  105.88-111.00 -60.00   52
  6  \w     80.00 106.00   1.00    4.00    --  105.88 -94.00  30.00   26
  7  \w     50.00 133.00   1.00    4.00    --  105.88 -77.00 -60.00   83
  8  \w     86.00 133.00   1.00    4.00    --  105.88  30.00 -60.00   47
  9  \w    126.00 160.00   1.00    4.00    --  105.88  30.00 -30.00   34
 10  \w    130.00 165.00   1.00    4.00    --  105.88  77.00  30.00   35
 11  \w    127.00 169.00   1.00    4.00    --  105.88  77.00  90.00   42
 12  \w    125.00 157.00   1.00    4.00    --  105.88  77.00 150.00   32
 13  \w    124.00 172.00   1.00    4.00    --  105.88  77.00 120.00   48
 14  \w    120.00 172.00   1.00    4.00    --  105.88  77.00  60.00   52
 15  \w    124.00 169.00   1.00    4.00    --  105.88  77.00   0.00   45
 16  \w    126.00 171.00   1.00    4.00    --  105.88  77.00 -90.00   45
 17  \w    124.00 173.00   1.00    4.00    --  105.88  77.00-150.00   49
 18  \w    126.00 170.00   1.00    4.00    --  105.88  77.00-180.00   44
 19  \w    125.00 156.00   1.00    4.00    --  105.88  77.00-120.00   31
 20  \w    112.00 173.00   1.00    4.00    --  105.88  77.00 -30.00   61
 21  \w     89.00 115.00   1.00    4.00    --  105.88  61.00 120.00   26
 22  \w     88.00 125.00   1.00    4.00    --  105.88  61.00  90.00   37
 23  \w     91.00 117.00   1.00    4.00    --  105.88  61.00  30.00   26
 24  \w     89.00 115.00   1.00    4.00    --  105.88  61.00   0.00   26
 25  \w     84.00 118.00   1.00    4.00    --  105.88  30.00   0.00   34
 26  \w     88.00 116.00   1.00    4.00    --  105.88  61.00  60.00   28
 27  \w     84.00 113.00   1.00    4.00    --  105.88  30.00  90.00   29
 28  \w     79.00 104.00   1.00    4.00    --  105.88  77.00  60.00   25
 29  \w     79.00 105.00   1.00    4.00    --  105.88  77.00  90.00   26
 30  \w     79.00 105.00   1.00    4.00    --  105.88  77.00 120.00   26
 31  \w     79.00 108.00   1.00    4.00    --  105.88  77.00 150.00   29
 32  \w     84.00 116.00   1.00    4.00    --  105.88  30.00 150.00   32
 33  \w     84.00 109.00   1.00    4.00    --  105.88  30.00  60.00   25
 34  \w     85.00 113.00   1.00    4.00    --  105.88  30.00  30.00   28
 35  \w     80.00 106.00   1.00    4.00    --  105.88  77.00  30.00   26
 36  \w     79.00 105.00   1.00    4.00    --  105.88  77.00   0.00   26
 37  \w     79.00 104.00   1.00    4.00    --  105.88  77.00 -30.00   25
 38  \w     88.00 113.00   1.00    4.00    --  105.88  61.00 -60.00   25
 39  \w     88.00 114.00   1.00    4.00    --  105.88  61.00 -90.00   26
 40  \w     79.00 105.00   1.00    4.00    --  105.88  77.00-150.00   26
 41  \w     88.00 128.00   1.00    4.00    --  105.88  61.00-150.00   40
 42  \w     88.00 131.00   1.00    4.00    --  105.88  30.00-150.00   43
 43  \w     84.00 113.00   1.00    4.00    --  105.88  30.00 -90.00   29
 44  \w     79.00 105.00   1.00    4.00    --  105.88  77.00 -60.00   26
 45  \w     79.00 105.00   1.00    4.00    --  105.88  77.00 -90.00   26
 46  \w     79.00 104.00   1.00    4.00    --  105.88  77.00-120.00   25
 47  \w     86.00 114.00   1.00    4.00    --  105.88  30.00-180.00   28
 48  \w     79.00 105.00   1.00    4.00    --  105.88  77.00-180.00   26
 49  \w     41.00  95.00   1.00    1.00    --   34.73  77.00-120.00   54
 50  \w     72.00  98.00   1.00    1.00    --   34.73  77.00 -90.00   26
 51  \w     69.00 101.00   1.00    1.00    --   34.73  57.00 -30.00   32
 52  \w     66.00 100.00   1.00    1.00    --   34.73  77.00   0.00   34
 53  \w     71.00 101.00   1.00    1.00    --   34.73  77.00  60.00   30
 54  \w     75.00 101.00   1.00    1.00    --   34.73  77.00  90.00   26
 55  \w     84.00 110.00   1.00    4.00    --  105.88  30.00 -30.00   26
 56  \w     69.00  94.00   1.00    1.00    --   34.73  38.00-150.00   25
 57  \w     16.00  44.00   1.00    1.00    --   34.73  38.00-150.00   28
 58  \w     13.00  43.00   1.00    1.00    --   34.73  77.00 -90.00   30
 59  \w     10.00  37.00   1.00    1.00    --   34.73  77.00-120.00   27
 60  \w     19.00  45.00   1.00    1.00    --   34.73  57.00 -30.00   26
 61  \w      8.00  56.00   1.00    1.00    --   34.73  77.00   0.00   48
 62  \w      9.00  55.00   1.00    1.00    --   34.73  77.00  90.00   46
 63  \w      8.00  34.00   1.00    1.00    --   34.73  77.00  60.00   26
 64  \w      8.00 100.00   1.00    1.00    --   34.73  77.00 150.00   92
 65  \w     38.00 126.00   1.00    4.00    --  105.88 -77.00 150.00   88
 66  \w     38.00  63.00   1.00    4.00    --  105.88 -94.00  30.00   25
 67  \w     37.00 106.00   1.00    4.00    --  105.88 -94.00 120.00   69
 68  \w    -27.00  44.00   1.00    1.00    --   34.73 -57.00-150.00   71
 69  \w    -31.00  50.00   1.00    1.00    --   34.73 -57.00 -60.00   81
 70  \w    -32.00  50.00   1.00    1.00    --   34.73 -57.00 120.00   82
 71  \w    -44.00 -19.00   1.00    1.00    --  -34.73 125.00  30.00   25
 72  \w    -95.00 -52.00   1.00    1.00    --  -34.73 -19.00 -30.00   43
 73  \w    -88.00 -51.00   1.00    1.00    --  -34.73 125.00  30.00   37
;
_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      -0.0349169000
_diffrn_orient_matrix_UB_12      -0.0579389000
_diffrn_orient_matrix_UB_13      -0.0933940000
_diffrn_orient_matrix_UB_21      0.2043072000
_diffrn_orient_matrix_UB_22      -0.0527622000
_diffrn_orient_matrix_UB_23      0.0214943000
_diffrn_orient_matrix_UB_31      -0.1397885000
_diffrn_orient_matrix_UB_32      -0.0883741000
_diffrn_orient_matrix_UB_33      0.0180036000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0694
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            4733
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.731
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17047
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_description       block
_exptl_crystal_F_000             486
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;

;
_refine_diff_density_max         1.084
_refine_diff_density_min         -0.853
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4733
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0923
_refine_ls_R_factor_gt           0.0811
_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^)+(0.1579P)^2^+0.8576P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2376
_refine_ls_wR_factor_ref         0.2490
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3926
_reflns_number_total             4733
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03303_si_002.cif
_cod_data_source_block           exp_647-sr
_cod_original_cell_volume        1339.71(7)
_cod_database_code               4037841
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C60 H120 O4 S3'
_shelx_estimated_absorpt_t_max   0.611
_shelx_estimated_absorpt_t_min   0.495
_reflns_odcompleteness_completeness 99.87
_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:
 C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C6(H6), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_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 4.842
_oxdiff_exptl_absorpt_empirical_full_min 0.349