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_7156474
_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 Cl O'
_chemical_formula_sum            'C23 H17 Cl O'
_chemical_formula_weight         344.82
_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
_audit_creation_date             2018-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-06-05 deposited with the CCDC.
2018-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1740(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.23180(10)
_cell_length_b                   19.0611(3)
_cell_length_c                   30.5102(4)
_cell_measurement_reflns_used    12167
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.7930
_cell_measurement_theta_min      2.3530
_cell_volume                     3609.39(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -18.00  15.00   0.50    4.56    --  -41.35 101.00 137.00   66
  2  \w    -69.00 -22.00   0.50    4.56    --  -41.35 101.00 137.00   94
  3  \w     72.00  98.00   0.50   18.24    --  101.00-101.00  32.00   52
  4  \w    120.00 146.00   0.50   18.24    --  101.00 101.00 137.00   52
  5  \w    -99.00 -21.00   0.50    4.56    --  -41.35 -65.00  30.00  156
  6  \w   -104.00 -75.00   0.50    4.56    --  -41.35 -32.00-180.00   58
  7  \w    -69.00 -42.00   0.50    4.56    --  -41.35 -32.00  60.00   54
  8  \w    -66.00 -37.00   0.50    4.56    --  -41.35 -32.00-180.00   58
  9  \w   -103.00 -73.00   0.50    4.56    --  -41.35 -32.00  60.00   60
 10  \w      2.00  37.00   0.50    4.56    --   41.35-101.00  32.00   70
 11  \w    -21.00  27.00   0.50    4.56    --   41.35 -32.00-120.00   96
 12  \w    -22.00  19.00   0.50    4.56    --   41.35 -77.00 -30.00   82
 13  \w     44.00 101.00   0.50    4.56    --   41.35  43.00 120.00  114
 14  \w     25.00 101.00   0.50    4.56    --   41.35  65.00 150.00  152
 15  \w     25.00  64.00   0.50    4.56    --   41.35 -77.00 -30.00   78
 16  \w      6.00  32.00   0.50    4.56    --   41.35 -54.00 -30.00   52
 17  \w     51.00  76.00   0.50    4.56    --   41.35-101.00  32.00   50
 18  \w     34.00  59.00   0.50    4.56    --   41.35 -54.00 -30.00   50
 19  \w    -20.00   6.00   0.50    4.56    --   41.35 -43.00  60.00   52
 20  \w     28.00  53.00   0.50    4.56    --   41.35 -43.00  60.00   50
 21  \w     88.00 114.00   0.50   18.24    --  101.00 -42.00 150.00   52
 22  \w     92.00 146.00   0.50   18.24    --  101.00  33.00 150.00  108
 23  \w     40.00  68.00   0.50   18.24    --  101.00 -42.00 150.00   56
 24  \w     39.00  64.00   0.50   18.24    --  101.00-133.00 150.00   50
 25  \w     41.00 132.00   0.50   18.24    --  101.00 -93.00-120.00  182
 26  \w     55.00  81.00   0.50   18.24    --  101.00 -17.00 -30.00   52
 27  \w    129.00 157.00   0.50   18.24    --  101.00  33.00-120.00   56
 28  \w    100.00 126.00   0.50   18.24    --  101.00  33.00-120.00   52
 29  \w     43.00 119.00   0.50   18.24    --  101.00 -77.00  60.00  152
 30  \w     99.00 143.00   0.50   18.24    --  101.00  25.00   0.00   88
 31  \w     41.00 110.00   0.50   18.24    --  101.00 -33.00 -30.00  138
 32  \w     42.00  98.00   0.50   18.24    --  101.00 -77.00  30.00  112
 33  \w     52.00  82.00   0.50   18.24    --  101.00-111.00-150.00   60
 34  \w     36.00 116.00   0.50   18.24    --  101.00 -93.00  30.00  160
 35  \w    106.00 150.00   0.50   18.24    --  101.00  33.00  90.00   88
 36  \w     83.00 148.00   0.50   18.24    --  101.00 111.00 -60.00  130
 37  \w    124.00 157.00   0.50   18.24    --  101.00  77.00 120.00   66
 38  \w     91.00 116.00   0.50   18.24    --  101.00 -50.00   0.00   50
 39  \w     42.00  67.00   0.50   18.24    --  101.00 -50.00   0.00   50
 40  \w     91.00 155.00   0.50   18.24    --  101.00  17.00  60.00  128
 41  \w     76.00 112.00   0.50   18.24    --  101.00  77.00 120.00   72
 42  \w     72.00 115.00   0.50   18.24    --  101.00 -59.00  60.00   86
 43  \w     89.00 114.00   0.50   18.24    --  101.00 -87.00  60.00   50
 44  \w     88.00 153.00   0.50   18.24    --  101.00  42.00 -60.00  130
 45  \w      5.00  30.00   0.50    4.56    --   41.35-101.00  32.00   50
;
_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      -0.0720141000
_diffrn_orient_matrix_UB_12      -0.0066933000
_diffrn_orient_matrix_UB_13      -0.0494359000
_diffrn_orient_matrix_UB_21      -0.0656752000
_diffrn_orient_matrix_UB_22      -0.0768323000
_diffrn_orient_matrix_UB_23      0.0070611000
_diffrn_orient_matrix_UB_31      -0.2283342000
_diffrn_orient_matrix_UB_32      0.0243098000
_diffrn_orient_matrix_UB_33      0.0085649000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0115
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            7095
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.210
_diffrn_reflns_theta_min         2.737
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.911
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018)
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    1.269
_exptl_crystal_description       prism
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         7095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0525
_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^)+(0.1195P)^2^+0.4248P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1530
_refine_ls_wR_factor_ref         0.1576
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6209
_reflns_number_total             7095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01985a2.cif
_cod_data_source_block           7071-8899-ima065_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 7156474--7156479.cif.'
_cod_database_code               7156474
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C12 O2 Cl1 H24'
_shelx_estimated_absorpt_t_max   0.701
_shelx_estimated_absorpt_t_min   0.607
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.37(5)
 0.63(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00D(H00D), C00G(H00G), C00H(H00H), C00I(H00I),
 C00J(H00J), C00K(H00K), C00L(H00L), C00O(H00O), C00P(H00P), C00Q(H00Q),
 C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C012(H012), C013(H013),
 C014(H014), C015(H015), C016(H016), C018(H018), C019(H019), C01A(H01A),
 C01B(H01B), C01C(H01C), C01D(H01D), C01E(H01E)
;
_shelx_res_checksum              45731
_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 1.800
_oxdiff_exptl_absorpt_empirical_full_min 0.529
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 0.4687\% 
 around [0.12 0.94 -0.31] (reciprocal) or [0.76 0.64 -0.07] (direct)
;