Arylative double bond transposition of allylic alcohols via silicon-tethered intramolecular benzyne–ene reactions
Kato, Ritsuki; Sakaue, Takaya; Tawatari, Tsukasa; Takasu, Kiyosei; Takikawa, Hiroshi; Chemical Communications 61 (2025) 8347–8350; doi:10.1039/D5CC01918D

data_7134496
_publ_section_title
;
 Arylative double bond transposition of allylic alcohols via
 silicon-tethered intramolecular benzyne--ene reactions
;
_journal_issue                   46
_journal_name_full               'Chemical Communications'
_journal_page_first              8347
_journal_page_last               8350
_journal_paper_doi               10.1039/D5CC01918D
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         '0.5(C22 H32 O Si)'
_chemical_formula_sum            'C11 H16 O0.5 Si0.5'
_chemical_formula_weight         170.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-03-24
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2025-04-05 deposited with the CCDC.	2025-05-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.142(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5045(4)
_cell_length_b                   10.0122(4)
_cell_length_c                   11.2032(4)
_cell_measurement_reflns_used    6873
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.8080
_cell_measurement_theta_min      5.2020
_cell_volume                     987.48(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3-ac4 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.971
_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   -136.00  43.00   0.50    0.50    --  -46.70  14.00  16.00  358
  2  \w   -187.00  -8.00   0.50    0.50    --  -97.40  14.00  16.00  358
  3  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00  90.00   92
  4  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00  90.00  116
  5  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00   0.00   92
  6  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00   0.00  116
  7  \w    -77.00  21.00   0.50    0.50    --    5.00  14.00  16.00  196
  8  \w    -82.00 -42.00   0.50    0.50    --  -97.40  60.00  53.80   80
  9  \w   -112.00 -86.00   0.50    0.50    --  -97.40  59.00  94.71   52
 10  \w   -186.00  -8.00   0.50    0.50    --  -97.40  10.00 120.00  356
 11  \w   -186.00 -63.00   0.50    0.50    --  -97.40  60.00 168.57  246
 12  \w   -141.00 -98.00   0.50    0.50    --  -97.40  60.00  53.80   86
 13  \w   -181.00 -20.00   0.50    0.50    --  -97.40  47.00 178.67  322
 14  \w   -187.00-108.00   0.50    0.50    --  -97.40  60.00  -7.77  158
 15  \w   -143.00-117.00   0.50    0.50    --  -97.40  59.00  94.71   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0692764000
_diffrn_orient_matrix_UB_12      -0.0097593000
_diffrn_orient_matrix_UB_13      -0.1480028000
_diffrn_orient_matrix_UB_21      -0.1572690000
_diffrn_orient_matrix_UB_22      0.0341221000
_diffrn_orient_matrix_UB_23      0.0012814000
_diffrn_orient_matrix_UB_31      0.0317790000
_diffrn_orient_matrix_UB_32      0.1500330000
_diffrn_orient_matrix_UB_33      -0.0094862000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6815
_diffrn_reflns_point_group_measured_fraction_full 0.766
_diffrn_reflns_point_group_measured_fraction_max 0.740
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.084
_diffrn_reflns_theta_min         4.261
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65054
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_description       plate
_exptl_crystal_F_000             372
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.484
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 796 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(5)
_refine_ls_extinction_coef       0.010(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.160
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         2886
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0981P)^2^+1.0847P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1451
_refine_ls_wR_factor_ref         0.1780
_reflns_Friedel_coverage         0.437
_reflns_Friedel_fraction_full    0.510
_reflns_Friedel_fraction_max     0.479
_reflns_number_gt                2730
_reflns_number_total             2886
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01918d2.cif
_cod_data_source_block           220302rk_auto
_cod_depositor_comments
'Adding full bibliography for 7134496--7134497.cif.'
_cod_original_cell_volume        987.48(7)
_cod_original_formula_sum        'C11 H16 O0.50 Si0.50'
_cod_database_code               7134496
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.901
_reflns_odcompleteness_completeness 99.36
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C005(H005), C00B(H00F), C00C(H00G), C00E(H00H), C00I(H00O), C00N(H00Z)
2.b Secondary CH2 refined with riding coordinates:
 C007(H00A,H00B), C00F(H00I,H00J)
2.c Aromatic/amide H refined with riding coordinates:
 C004(H004), C006(H006), C00G(H00K), C00J(H00P)
2.d Idealised Me refined as rotating group:
 C008(H00C,H00D,H00E), C00H(H00L,H00M,H00N), C00K(H00Q,H00R,H00S), C00L(H00T,
 H00U,H00V), C00M(H00W,H00X,H00Y), C00O(H00,H,HA)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 2.552
_oxdiff_exptl_absorpt_empirical_full_min 0.550