Hydroarylation of unsaturated carbon-carbon bonds in cross-conjugated enynones under the action of superacid CF<sub>3</sub>SO<sub>3</sub>H or acidic zeolite HUSY. Reaction mechanism and DFT study on cationic intermediate species.
Aleksandrova, Maiia I.; Lozovskiy, Stanislav V.; Saulnier, Steve; Golovanov, Alexander A.; Boyarskaya, Irina A.; Vasilyev, Aleksander V.; Organic & biomolecular chemistry 16 (2018) 7891–7902; doi:10.1039/c8ob01985a

data_7156478
_publ_section_title
;
 Hydroarylation of unsaturated carbon-carbon bonds in cross-conjugated
 enynones under the action of superacid CF<sub>3</sub>SO<sub>3</sub>H or
 acidic zeolite HUSY. Reaction mechanism and DFT study on cationic
 intermediate species.
;
_journal_issue                   42
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7891
_journal_page_last               7902
_journal_paper_doi               10.1039/c8ob01985a
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C21 H16 O S'
_chemical_formula_sum            'C21 H16 O S'
_chemical_formula_weight         316.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-06-05 deposited with the CCDC.
2018-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6982(5)
_cell_length_b                   12.0382(7)
_cell_length_c                   17.5134(12)
_cell_measurement_reflns_used    5137
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.6020
_cell_measurement_theta_min      4.3850
_cell_volume                     1623.01(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -95.00 -49.00   0.50    2.01    --  -41.35 -50.00 -34.00   92
  2  \w     -7.00  18.00   0.50    2.01    --  -41.35  95.00 -26.00   50
  3  \w    -61.00 -36.00   0.50    2.01    --  -41.35  95.00 -26.00   50
  4  \w    -23.00  19.00   0.50    2.01    --  -41.35  50.00 111.00   84
  5  \w     21.00  46.00   0.50    2.01    --   41.35 -82.00 114.00   50
  6  \w     53.00  78.00   0.50    2.01    --   41.35  50.00 111.00   50
  7  \w      4.00  33.00   0.50    2.01    --   41.35 -95.00-137.00   58
  8  \w    -16.00   9.00   0.50    2.01    --   41.35 -50.00 -34.00   50
  9  \w     99.00 125.00   0.50    8.05    --  101.00  50.00 111.00   52
 10  \w    118.00 151.00   0.50    8.05    --  101.00  82.00-123.00   66
 11  \w    111.00 155.00   0.50    8.05    --  101.00  95.00 -26.00   88
 12  \w     46.00  72.00   0.50    8.05    --  101.00 -95.00-137.00   52
 13  \w     74.00  99.00   0.50    8.05    --  101.00 -82.00 114.00   50
 14  \w     40.00 115.00   0.50    8.05    --  101.00 -50.00 -34.00  150
 15  \w    -93.00 -35.00   0.50    2.01    --  -41.35 -32.00-180.00  116
 16  \w    -58.00  22.00   0.50    2.01    --  -41.35  65.00 150.00  160
 17  \w    -23.00   2.00   0.50    2.01    --  -41.35  82.00-123.00   50
 18  \w     46.00 105.00   0.50    2.01    --   41.35  32.00-180.00  118
 19  \w    107.00 157.00   0.50    8.05    --  101.00  33.00-120.00  100
 20  \w     88.00 153.00   0.50    8.05    --  101.00  42.00 150.00  130
 21  \w     84.00 120.00   0.50    8.05    --  101.00 -59.00-120.00   72
 22  \w     37.00 115.00   0.50    8.05    --  101.00 -68.00-150.00  156
 23  \w     39.00  69.00   0.50    8.05    --  101.00 -87.00  30.00   60
 24  \w     83.00 126.00   0.50    8.05    --  101.00 -87.00  30.00   86
 25  \w     43.00  78.00   0.50    8.05    --  101.00 -59.00-120.00   70
 26  \w    107.00 132.00   0.50    8.05    --  101.00  17.00  60.00   50
 27  \w     70.00  95.00   0.50    8.05    --  101.00 -95.00-137.00   50
 28  \w     39.00  65.00   0.50    2.01    --   41.35  32.00-150.00   52
 29  \w     99.00 152.00   0.50    8.05    --  101.00  33.00  30.00  106
 30  \w    118.00 147.00   0.50    8.05    --  101.00 178.00-120.00   58
 31  \w     87.00 113.00   0.50    8.05    --  101.00-111.00 -30.00   52
 32  \w     64.00 113.00   0.50    8.05    --  101.00-133.00 150.00   98
 33  \w     38.00  91.00   0.50    8.05    --  101.00 178.00-120.00  106
 34  \w     35.00  60.00   0.50    8.05    --  101.00-111.00 -30.00   50
 35  \w    128.00 157.00   0.50    8.05    --  101.00  93.00 -30.00   58
 36  \w     48.00  83.00   0.50    8.05    --  101.00 -25.00 150.00   70
 37  \w     85.00 111.00   0.50    8.05    --  101.00  59.00-120.00   52
 38  \w     49.00 108.00   0.50    8.05    --  101.00 -25.00 -30.00  118
 39  \w    -67.00 -37.00   0.50    2.01    --  -41.35  82.00-123.00   60
 40  \w    -74.00 -31.00   0.50    2.01    --  -41.35 104.00 120.00   86
 41  \w    -46.00 -20.00   0.50    2.01    --  -41.35  21.00 150.00   52
 42  \w    -12.00  14.00   0.50    2.01    --  -41.35 104.00 120.00   52
 43  \w    -57.00 -15.00   0.50    2.01    --  -41.35  54.00  90.00   84
 44  \w     -1.00  24.00   0.50    2.01    --  -41.35  82.00-123.00   50
 45  \w     -5.00  27.00   0.50    2.01    --  -41.35  21.00 150.00   64
 46  \w      8.00  54.00   0.50    2.01    --   41.35 -43.00 -30.00   92
 47  \w     54.00  91.00   0.50    2.01    --   41.35-138.00  30.00   74
 48  \w     25.00  75.00   0.50    2.01    --   41.35  54.00 -60.00  100
 49  \w     25.00  70.00   0.50    2.01    --   41.35-104.00 -60.00   90
 50  \w     87.00 113.00   0.50    8.05    --  101.00  17.00 -60.00   52
 51  \w     86.00 111.00   0.50    8.05    --  101.00 -42.00 150.00   50
 52  \w     53.00  87.00   0.50    8.05    --  101.00 -68.00  60.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0959826000
_diffrn_orient_matrix_UB_12      0.0175744000
_diffrn_orient_matrix_UB_13      0.0762494000
_diffrn_orient_matrix_UB_21      -0.0766195000
_diffrn_orient_matrix_UB_22      -0.1179171000
_diffrn_orient_matrix_UB_23      -0.0057144000
_diffrn_orient_matrix_UB_31      0.1582046000
_diffrn_orient_matrix_UB_32      -0.0463580000
_diffrn_orient_matrix_UB_33      0.0434245000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            11405
_diffrn_reflns_point_group_measured_fraction_full 0.928
_diffrn_reflns_point_group_measured_fraction_max 0.916
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.940
_diffrn_reflns_theta_min         4.457
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.768
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86138
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
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    1.295
_exptl_crystal_description       prism
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.494
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 1027 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.30(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2925
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0508
_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^)+(0.0405P)^2^+1.4819P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1205
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.850
_reflns_Friedel_fraction_max     0.829
_reflns_number_gt                2681
_reflns_number_total             2925
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01985a2.cif
_cod_data_source_block           9176_z-6
_cod_depositor_comments
'Adding full bibliography for 7156474--7156479.cif.'
_cod_database_code               7156478
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C21 O S'
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.708
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{S1A, C10}
{S1, C7}
3. Restrained distances
 C6-S1A
 1.65 with sigma of 0.00002
4. Others
 Sof(S1)=Sof(H8A)=Sof(H8B)=Sof(C10)=Sof(H7)=1-FVAR(1)
 Sof(S1A)=Sof(H9A)=Sof(H9B)=Sof(H10)=Sof(C7)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C16(H16), C13(H13), C15(H15), C14(H14), C2(H2), C18(H18),
 C12(H12), C22(H22), C19(H19), C21(H21), C20(H20), C8(H8A), C8(H8B), C9(H9A),
 C9(H9B), C10(H10), C7(H7)
;
_shelx_res_checksum              19885
_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 2.330
_oxdiff_exptl_absorpt_empirical_full_min 0.545