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_7156479
_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_absolute_configuration unk
_chemical_formula_moiety         'C23 H18 O'
_chemical_formula_sum            'C23 H18 O'
_chemical_formula_weight         310.37
_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             2017-12-13
_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                   7.75140(10)
_cell_length_b                   12.0257(2)
_cell_length_c                   17.7094(3)
_cell_measurement_reflns_used    8400
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.4440
_cell_measurement_theta_min      4.3960
_cell_volume                     1650.80(4)
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_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    -69.00 -23.00   1.00    1.00    --  -40.38 -38.00 -30.00   46
  2  \w   -116.00 -28.00   1.00    1.00    --  -40.38 -38.00 120.00   88
  3  \w     94.00 128.00   1.00    1.00    --   40.38 178.00-120.00   34
  4  \w     94.00 119.00   1.00    1.00    --   40.38 178.00   0.00   25
  5  \w     38.00 173.00   1.00    1.00    --  113.00   0.00-180.00  135
  6  \w     76.00 103.00   1.00    1.00    --  113.00 -95.00 -60.00   27
  7  \w     68.00 107.00   1.00    1.00    --  113.00 -95.00  30.00   39
  8  \w     36.00  63.00   1.00    1.00    --  113.00 -95.00 -60.00   27
  9  \w     30.00  82.00   1.00    1.00    --  113.00 -95.00   0.00   52
 10  \w     35.00  62.00   1.00    1.00    --  113.00 -95.00  30.00   27
 11  \w     63.00 113.00   1.00    1.00    --   40.38 178.00  30.00   50
 12  \w     63.00 105.00   1.00    1.00    --  113.00 -95.00 120.00   42
 13  \w     41.00  68.00   1.00    1.00    --  113.00 -95.00-150.00   27
 14  \w     81.00 107.00   1.00    1.00    --  113.00 -95.00-150.00   26
 15  \w     75.00 101.00   1.00    1.00    --  113.00 -95.00  60.00   26
 16  \w     49.00 115.00   1.00    1.00    --  113.00 -45.00 -30.00   66
 17  \w     99.00 139.00   1.00    1.00    --  113.00 -15.00  90.00   40
 18  \w    -97.00 -45.00   1.00    1.00    --  -40.38 178.00-120.00   52
 19  \w    -74.00  31.00   1.00    1.00    --  -40.38  19.00 -60.00  105
 20  \w     65.00 125.00   1.00    1.00    --   40.38 178.00-180.00   60
 21  \w     45.00 143.00   1.00    1.00    --  113.00 -61.00 120.00   98
 22  \w    141.00 177.00   1.00    1.00    --  113.00  61.00-180.00   36
 23  \w     60.00 112.00   1.00    1.00    --  113.00 -45.00  30.00   52
 24  \w     92.00 136.00   1.00    1.00    --  113.00  61.00-180.00   44
 25  \w     98.00 125.00   1.00    1.00    --  113.00  45.00 150.00   27
 26  \w     66.00 115.00   1.00    1.00    --  113.00-112.00 -90.00   49
 27  \w     93.00 142.00   1.00    1.00    --  113.00 -30.00 150.00   49
 28  \w    105.00 134.00   1.00    1.00    --  113.00 112.00-150.00   29
 29  \w    148.00 174.00   1.00    1.00    --  113.00 112.00-150.00   26
 30  \w     43.00  69.00   1.00    1.00    --  113.00-112.00  30.00   26
 31  \w     79.00 115.00   1.00    1.00    --  113.00-112.00  30.00   36
 32  \w     53.00  79.00   1.00    1.00    --  113.00 -30.00 150.00   26
 33  \w     30.00  69.00   1.00    1.00    --  113.00 -95.00 -30.00   39
 34  \w     41.00  91.00   1.00    1.00    --  113.00 -61.00-120.00   50
 35  \w    144.00 176.00   1.00    1.00    --  113.00  45.00 150.00   32
 36  \w     91.00 117.00   1.00    1.00    --  113.00-114.00 152.12   26
 37  \w     -3.00  22.00   1.00    1.00    --   36.00  91.00  95.45   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0373991000
_diffrn_orient_matrix_UB_12      0.1237927000
_diffrn_orient_matrix_UB_13      0.0148332000
_diffrn_orient_matrix_UB_21      0.0406522000
_diffrn_orient_matrix_UB_22      0.0266922000
_diffrn_orient_matrix_UB_23      -0.0831969000
_diffrn_orient_matrix_UB_31      -0.1911351000
_diffrn_orient_matrix_UB_32      -0.0187943000
_diffrn_orient_matrix_UB_33      -0.0204797000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_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            14542
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.960
_diffrn_reflns_theta_min         4.444
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.578
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42917
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       needle
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.153
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.2(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3045
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0436P)^2^+0.2371P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0747
_refine_ls_wR_factor_ref         0.0756
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2977
_reflns_number_total             3045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01985a2.cif
_cod_data_source_block           7071-8325_ima063
_cod_depositor_comments
'Adding full bibliography for 7156474--7156479.cif.'
_cod_database_code               7156479
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.893
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8(4)
 0.2(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C8(H8), C6(H6), C24(H24), C14(H14), C4(H4), C5(H5),
 C18(H18), C2(H2), C20(H20), C3(H3), C17(H17), C16(H16), C15(H15), C23(H23),
 C21(H21), C22(H22)
;
_shelx_res_checksum              99855
_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 3.082
_oxdiff_exptl_absorpt_empirical_full_min 0.404