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_7134497
_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_formula_moiety         'C23 H30 O Si'
_chemical_formula_sum            'C23 H30 O Si'
_chemical_formula_weight         350.56
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-04-05
_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                 108.960(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.62484(17)
_cell_length_b                   37.0647(5)
_cell_length_c                   7.72583(13)
_cell_measurement_reflns_used    23328
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.7490
_cell_measurement_theta_min      2.3170
_cell_volume                     2064.96(7)
_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
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -84.00 -38.00   0.50    0.50    --    5.00  60.00 120.00   92
  2  \w    -84.00  94.00   0.50    0.50    --    5.00  30.00 150.00  356
  3  \w   -187.00 -33.00   0.50    0.50    --  -97.40  55.00  -4.01  308
  4  \w   -187.00 -26.00   0.50    0.50    --  -97.40  50.00  90.00  322
  5  \w   -187.00 -38.00   0.50    0.50    --  -97.40  60.00 149.67  298
  6  \w   -187.00  -8.00   0.50    0.50    --  -97.40  14.00 172.45  358
  7  \w   -187.00 -38.00   0.50    0.50    --  -97.40  60.00  55.39  298
  8  \w   -136.00  42.00   0.50    0.50    --  -46.90  32.00 170.82  356
  9  \w      4.00  42.00   0.50    0.50    --  -46.90  44.00   8.90   76
 10  \w   -187.00  -8.00   0.50    0.50    --  -97.40   0.00   0.00  358
 11  \w   -187.00  -8.00   0.50    0.50    --  -97.40  18.00  -8.02  358
 12  \w   -187.00  -8.00   0.50    0.50    --  -97.40  40.00 120.00  358
 13  \w   -187.00  -8.00   0.50    0.50    --  -97.40  43.00  52.69  358
 14  \w   -187.00  -8.00   0.50    0.50    --  -97.40  44.00 179.29  358
 15  \w   -187.00 -38.00   0.50    0.50    --  -97.40  60.00 179.95  298
 16  \w     38.00  94.00   0.50    0.50    --    5.00  60.00  90.00  112
 17  \w   -136.00  42.00   0.50    0.50    --  -46.90  40.00  90.00  356
 18  \w   -187.00  -8.00   0.50    0.50    --  -97.40  41.00  -6.93  358
 19  \w   -187.00 -46.00   0.50    0.50    --  -97.40  40.00  30.00  282
;
_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      -0.0703524000
_diffrn_orient_matrix_UB_12      0.0144519000
_diffrn_orient_matrix_UB_13      -0.1976588000
_diffrn_orient_matrix_UB_21      0.0664264000
_diffrn_orient_matrix_UB_22      0.0381776000
_diffrn_orient_matrix_UB_23      0.0707026000
_diffrn_orient_matrix_UB_31      0.1902119000
_diffrn_orient_matrix_UB_32      -0.0078914000
_diffrn_orient_matrix_UB_33      -0.0210359000
_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  0.0510
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            36726
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.080
_diffrn_reflns_theta_min         2.384
_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    1.039
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66463
_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    1.128
_exptl_crystal_description       plate
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.637
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         4024
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0526
_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^)+(0.0408P)^2^+2.6386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1274
_refine_ls_wR_factor_ref         0.1281
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3875
_reflns_number_total             4024
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01918d2.cif
_cod_data_source_block           250405ts3_auto
_cod_depositor_comments
'Adding full bibliography for 7134496--7134497.cif.'
_cod_database_code               7134497
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H30OSi
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.681
_reflns_odcompleteness_completeness 99.87
_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:
 C8(H8), C18(H18), C45(H45), C50(H50)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C25(H25), C30(H30), C52(H52), C57(H57), C69(H69), C78(H78),
 C79(H79), C85(H85)
2.c X=CH2 refined with riding coordinates:
 C66(H66A,H66B)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C64(H64A,H64B,H64C), C75(H75A,H75B,
 H75C), C87(H87A,H87B,H87C)
;
_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 1.629
_oxdiff_exptl_absorpt_empirical_full_min 0.500