Relative Reactivity of Benzothiophene-Fused Enediynes in the Bergman Cyclization.
Lyapunova, Anna G.; Danilkina, Natalia A.; Rumyantsev, Andrey M.; Khlebnikov, A. F.; Chislov, Mikhail V.; Starova, Galina L.; Sambuk, Elena V.; Govdi, Anastasia I.; Bräse, Stefan; Balova, Irina A.; The Journal of organic chemistry 83 (2018) 2788–2801; doi:10.1021/acs.joc.7b03258

data_4034955
_publ_section_title
;
 Relative Reactivity of Benzothiophene-Fused Enediynes in the Bergman
 Cyclization.
;
_journal_issue                   5
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2788
_journal_page_last               2801
_journal_paper_doi               10.1021/acs.joc.7b03258
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C19 H17 F S'
_chemical_formula_sum            'C19 H17 F S'
_chemical_formula_weight         296.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.745(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3050(3)
_cell_length_b                   13.9740(3)
_cell_length_c                   12.0297(4)
_cell_measurement_reflns_used    3998
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.2610
_cell_measurement_theta_min      4.9850
_cell_volume                     1481.23(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -44.00   32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000   90.0000 76

  2 omega    1.00   50.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354  -99.0000  -60.0000 49

  3 omega   36.00   89.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   60.0000 53

  4 omega   64.00  101.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -53.0000  118.7226 37

  5 omega   70.00   96.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000  150.0000 26

  6 omega   62.00   92.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  120.0000 30

  7 omega   57.00   82.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   90.0000 25

  8 omega   44.00   69.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  120.0000 25

  9 omega  109.00  157.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000   60.0000 48

 10 omega  134.00  160.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   30.0000 26

 11 omega  132.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000    0.0000 26

 12 omega   86.00  125.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000    0.0000 39

 13 omega   69.00  110.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000  -90.0000 41

 14 omega   54.00   84.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -30.0000 30

 15 omega   44.00   97.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -90.0000 53

 16 omega   46.00  110.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000 -150.0000 64

 17 omega   41.00   69.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000 -120.0000 28

 18 omega   47.00   91.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000    0.0000 44

 19 omega   41.00  102.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000   30.0000 61

 20 omega   36.00   80.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -180.0000 44

 21 omega   94.00  129.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000 -150.0000 35

 22 omega   94.00  171.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  150.0000 77

 23 omega  -39.00   24.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000 -180.0000 63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1508108000
_diffrn_orient_matrix_UB_12      0.0528724000
_diffrn_orient_matrix_UB_13      0.0583650000
_diffrn_orient_matrix_UB_21      -0.0808851000
_diffrn_orient_matrix_UB_22      0.0678903000
_diffrn_orient_matrix_UB_23      0.0614511000
_diffrn_orient_matrix_UB_31      0.0359224000
_diffrn_orient_matrix_UB_32      -0.0689282000
_diffrn_orient_matrix_UB_33      0.1053951000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9049
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.494
_diffrn_reflns_theta_min         5.009
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.941
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       prism
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.373
_refine_diff_density_min         -0.250
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2918
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0549P)^2^+0.5507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2614
_reflns_number_total             2918
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b03258_si_001.cif
_cod_data_source_block           103-5699-4534_agl-149
_cod_database_code               4034955
_chemical_oxdiff_formula         'C19 H17 F S'
_reflns_odcompleteness_completeness 93.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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:
 C6(H6A,H6B), C11(H11A,H11B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C17(H17)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C13(H13A,H13B,H13C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'