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_7156476
_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         'C23 H17 F O'
_chemical_formula_sum            'C23 H17 F O'
_chemical_formula_weight         328.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-15
_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                 99.406(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.20717(15)
_cell_length_b                   38.6061(11)
_cell_length_c                   14.5881(3)
_cell_measurement_reflns_used    14414
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.7140
_cell_measurement_theta_min      2.2280
_cell_volume                     3448.81(15)
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -78.00 -32.00   0.50    0.20    --  -41.35 136.00 -41.00   92
  2  \w    -71.00 -45.00   0.50    0.20    --  -41.35 133.00 140.00   52
  3  \w     11.00  36.00   0.50    0.20    --   41.35-133.00  71.00   50
  4  \w     30.00  55.00   0.50    0.20    --   41.35-136.00-106.00   50
  5  \w     88.00 113.00   0.50    0.43    --  101.00 136.00 -41.00   50
  6  \w     83.00 109.00   0.50    0.43    --  101.00-136.00-106.00   52
  7  \w     78.00 124.00   0.50    0.43    --  101.00-133.00  71.00   92
  8  \w    113.00 138.00   0.50    0.43    --  101.00 133.00 140.00   50
  9  \w   -104.00 -70.00   0.50    0.20    --  -41.35 -54.00  30.00   68
 10  \w    -64.00 -26.00   0.50    0.20    --  -41.35 -54.00  30.00   76
 11  \w    -49.00 -17.00   0.50    0.20    --  -41.35 -77.00-120.00   64
 12  \w   -104.00 -70.00   0.50    0.20    --  -41.35 -77.00-120.00   68
 13  \w    -19.00  53.00   0.50    0.20    --   41.35 -43.00  30.00  144
 14  \w     54.00  98.00   0.50    0.20    --   41.35  32.00 -30.00   88
 15  \w     17.00  92.00   0.50    0.20    --   41.35  77.00 120.00  150
 16  \w     27.00  53.00   0.50    0.20    --   41.35  54.00 120.00   52
 17  \w     24.00  62.00   0.50    0.20    --   41.35 -65.00 150.00   76
 18  \w     70.00  95.00   0.50    0.20    --   41.35-133.00  71.00   50
 19  \w    -15.00  41.00   0.50    0.20    --   41.35 -43.00-180.00  112
 20  \w     71.00  97.00   0.50    0.20    --   41.35  54.00 120.00   52
 21  \w     62.00  90.00   0.50    0.43    --  101.00-111.00-180.00   56
 22  \w     52.00 100.00   0.50    0.43    --  101.00 -50.00-150.00   96
 23  \w     43.00 132.00   0.50    0.43    --  101.00 -93.00-120.00  178
 24  \w     81.00 143.00   0.50    0.43    --  101.00  93.00   0.00  124
 25  \w     78.00 104.00   0.50    0.43    --  101.00 -25.00 -30.00   52
 26  \w     64.00 123.00   0.50    0.43    --  101.00 -68.00  30.00  118
 27  \w    125.00 151.00   0.50    0.43    --  101.00  17.00 -30.00   52
 28  \w     88.00 117.00   0.50    0.43    --  101.00  17.00 -30.00   58
 29  \w    132.00 157.00   0.50    0.43    --  101.00  33.00 -30.00   50
 30  \w     88.00 135.00   0.50    0.43    --  101.00  59.00 -30.00   94
 31  \w     32.00  80.00   0.50    0.43    --  101.00 -93.00   0.00   96
 32  \w     89.00 114.00   0.50    0.43    --  101.00 -93.00   0.00   50
 33  \w     37.00  67.00   0.50    0.43    --  101.00 -68.00 -60.00   60
 34  \w     99.00 156.00   0.50    0.43    --  101.00  33.00 -90.00  114
 35  \w     71.00 113.00   0.50    0.43    --  101.00 -59.00-150.00   84
 36  \w     80.00 136.00   0.50    0.43    --  101.00 111.00   0.00  112
 37  \w     36.00 100.00   0.50    0.43    --  101.00-111.00-120.00  128
 38  \w     76.00 109.00   0.50    0.43    --  101.00  77.00-180.00   66
 39  \w     84.00 154.00   0.50    0.43    --  101.00 133.00 150.00  140
 40  \w     95.00 121.00   0.50    0.43    --  101.00  33.00 -30.00   52
 41  \w    122.00 147.00   0.50    0.43    --  101.00  77.00-180.00   50
 42  \w     36.00 110.00   0.50    0.43    --  101.00 -33.00-180.00  148
 43  \w     88.00 113.00   0.50    0.43    --  101.00 136.00 -41.00   50
 44  \w    -66.00 -40.00   0.50    0.20    --  -41.35 -32.00  60.00   52
 45  \w    -34.00  -8.00   0.50    0.20    --  -41.35  32.00-180.00   52
 46  \w     -7.00  20.00   0.50    0.20    --  -41.35  32.00-180.00   54
 47  \w     61.00  87.00   0.50    0.20    --   41.35  32.00-180.00   52
 48  \w      2.00  38.00   0.50    0.20    --   41.35 -54.00  90.00   72
 49  \w     37.00  78.00   0.50    0.20    --   41.35  32.00-120.00   82
 50  \w     66.00 100.00   0.50    0.20    --   41.35  11.00-120.00   68
 51  \w     19.00  45.00   0.50    0.20    --   41.35  11.00-120.00   52
 52  \w     72.00  98.00   0.50    0.43    --  101.00 133.00 -60.00   52
 53  \w     81.00 110.00   0.50    0.43    --  101.00 -25.00  60.00   58
;
_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      0.0170356000
_diffrn_orient_matrix_UB_12      0.0109513000
_diffrn_orient_matrix_UB_13      0.1024785000
_diffrn_orient_matrix_UB_21      0.0070491000
_diffrn_orient_matrix_UB_22      -0.0383757000
_diffrn_orient_matrix_UB_23      0.0293267000
_diffrn_orient_matrix_UB_31      0.2508918000
_diffrn_orient_matrix_UB_32      0.0003340000
_diffrn_orient_matrix_UB_33      0.0098186000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            27840
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.967
_diffrn_reflns_theta_min         2.289
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64501
_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    1.265
_exptl_crystal_description       needle
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         6752
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0561P)^2^+0.8845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1103
_refine_ls_wR_factor_ref         0.1144
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5883
_reflns_number_total             6752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01985a2.cif
_cod_data_source_block           9137_avv363
_cod_depositor_comments
'Adding full bibliography for 7156474--7156479.cif.'
_cod_database_code               7156476
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'F O C30'
_reflns_odcompleteness_completeness 99.28
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C19A(H19A), C2A(H2A), C4(H4), C5(H5), C13A(H13A), C4A(H4A), C19(H19),
 C17(H17), C17A(H17A), C2(H2), C5A(H5A), C11(H11), C7(H7), C23(H23), C10(H10),
 C23A(H23A), C11A(H11A), C10A(H10A), C20A(H20A), C21A(H21A), C13(H13),
 C16A(H16A), C7A(H7A), C22(H22), C16(H16), C15(H15), C22A(H22A), C8(H8),
 C14(H14), C20(H20), C15A(H15A), C8A(H8A), C14A(H14A), C21(H21)
;
_shelx_res_checksum              32692
_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 1.731
_oxdiff_exptl_absorpt_empirical_full_min 0.493