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_7156475
_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         'C17 H13 F O2'
_chemical_formula_sum            'C17 H13 F O2'
_chemical_formula_weight         268.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_audit_update_record
;
2018-06-05 deposited with the CCDC.
2018-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.47(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.335(6)
_cell_length_b                   5.7303(10)
_cell_length_c                   7.3960(18)
_cell_measurement_reflns_used    886
_cell_measurement_temperature    100(3)
_cell_measurement_theta_max      75.5760
_cell_measurement_theta_min      5.7730
_cell_volume                     1284.4(5)
_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(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -66.00 -39.00   1.00   35.00    --  -40.38 178.00  30.00   27
  2  \w   -100.00 -40.00   1.00   35.00    --  -40.38 178.00  90.00   60
  3  \w   -100.00 -14.00   1.00   35.00    --  -40.38 -38.00-120.00   86
  4  \w    -66.00  36.00   1.00   35.00    --  -40.38  38.00  60.00  102
  5  \w     98.00 129.00   1.00   35.00    --   40.38 178.00  30.00   31
  6  \w     67.00 129.00   1.00   35.00    --   40.38 178.00-150.00   62
  7  \w     53.00 139.00   1.00   52.50    --  113.00  15.00 -60.00   86
  8  \w     72.00 109.00   1.00   52.50    --  113.00 -95.00  90.00   37
  9  \w     38.00 123.00   1.00   52.50    --  113.00 -45.00   0.00   85
 10  \w    122.00 166.00   1.00   52.50    --  113.00  77.00 -30.00   44
 11  \w     88.00 176.00   1.00   52.50    --  113.00  30.00-180.00   88
 12  \w     30.00 109.00   1.00   52.50    --  113.00 -95.00  30.00   79
 13  \w     57.00 146.00   1.00   52.50    --  113.00 178.00  30.00   89
 14  \w    111.00 149.00   1.00   52.50    --  113.00  45.00  60.00   38
 15  \w     37.00  64.00   1.00   52.50    --  113.00-112.00-180.00   27
 16  \w     36.00 111.00   1.00   52.50    --  113.00-112.00   0.00   75
 17  \w     81.00 173.00   1.00   52.50    --  113.00  77.00 120.00   92
 18  \w     58.00 109.00   1.00   52.50    --  113.00 -95.00-180.00   51
 19  \w     41.00 116.00   1.00   52.50    --  113.00 -61.00 150.00   75
;
_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      -0.0497019000
_diffrn_orient_matrix_UB_12      -0.0476656000
_diffrn_orient_matrix_UB_13      -0.0325615000
_diffrn_orient_matrix_UB_21      -0.0049513000
_diffrn_orient_matrix_UB_22      -0.0237505000
_diffrn_orient_matrix_UB_23      0.2056652000
_diffrn_orient_matrix_UB_31      -0.0095442000
_diffrn_orient_matrix_UB_32      0.2627622000
_diffrn_orient_matrix_UB_33      0.0130068000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1108
_diffrn_reflns_av_unetI/netI     0.0985
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            3924
_diffrn_reflns_point_group_measured_fraction_full 0.823
_diffrn_reflns_point_group_measured_fraction_max 0.820
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.846
_diffrn_reflns_theta_min         2.916
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58711
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       needle
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.484
_refine_diff_density_min         -0.453
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.2(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         1996
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1187
_refine_ls_R_factor_gt           0.0982
_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^)+(0.1906P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2545
_refine_ls_wR_factor_ref         0.2959
_reflns_Friedel_coverage         0.641
_reflns_Friedel_fraction_full    0.648
_reflns_Friedel_fraction_max     0.642
_reflns_number_gt                1473
_reflns_number_total             1996
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01985a2.cif
_cod_data_source_block           9202_ima052
_cod_depositor_comments
'Adding full bibliography for 7156474--7156479.cif.'
_cod_database_code               7156475
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Cl2 F C25'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.853
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.55
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C7(H7), C2(H2A), C5(H5), C11(H11), C9(H9), C4(H4), C13(H13),
 C10(H10), C16(H16), C8(H8), C17(H17)
2.b Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              30113
_olex2_date_sample_data_collection 2018-03-24
_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 3.052
_oxdiff_exptl_absorpt_empirical_full_min 0.506