Palladium-catalyzed synthesis of benzosilacyclobutenes via position-selective C(sp3)–H arylation
Hamada, Naoya; Hayashi, Daigo; Shintani, Ryo; Chemical Communications  (2023) –; doi:10.1039/D3CC00442B

data_7131804
_publ_section_title
;
 Palladium-catalyzed synthesis of benzosilacyclobutenes via
 position-selective C(sp3)--H arylation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC00442B
_journal_year                    2023
_chemical_formula_moiety         'C33 H42 O Si'
_chemical_formula_sum            'C33 H42 O Si'
_chemical_formula_weight         482.75
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-24 deposited with the CCDC.	2023-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                68.423(2)
_cell_angle_beta                 70.324(2)
_cell_angle_gamma                89.9840(10)
_cell_formula_units_Z            2
_cell_length_a                   10.3545(2)
_cell_length_b                   12.0752(2)
_cell_length_c                   12.5616(3)
_cell_measurement_reflns_used    16815
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      29.5180
_cell_measurement_theta_min      2.5830
_cell_volume                     1361.51(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.57a (Rigaku OD, 2023)'
_computing_data_collection
'DTREK_VERSION=d*TREK version 9.9.9.8 W9RSSI -- Oct 30 2013'
_computing_data_reduction        'CrysAlisPro 1.171.43.57a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      113.15
_diffrn_detector                 'PLATUS 200K area detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.876
_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   -102.00  78.00   0.50    5.00    --  -12.00  45.00 122.00  360
  2  \w    -62.00  78.00   0.50    5.00    --  -12.00  45.00  51.00  280
  3  \w    -71.00  78.00   0.50    5.00    --  -12.00  45.00 300.00  298
  4  \w    -62.00  71.00   0.50    5.00    --  -12.00  45.00 193.00  266
  5  \w    -59.50  30.00   0.50    5.00    --  -12.00  45.00 -20.00  179
  6  \w      8.00  57.50   0.50    5.00    --  -12.00  45.00  15.00   99
  7  \w    -61.00 -16.00   0.50    5.00    --  -12.00  45.00 264.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0070051000
_diffrn_orient_matrix_UB_12      0.0055070000
_diffrn_orient_matrix_UB_13      0.0559160000
_diffrn_orient_matrix_UB_21      0.0722656000
_diffrn_orient_matrix_UB_22      -0.0002724000
_diffrn_orient_matrix_UB_23      -0.0137849000
_diffrn_orient_matrix_UB_31      0.0113234000
_diffrn_orient_matrix_UB_32      0.0635672000
_diffrn_orient_matrix_UB_33      -0.0304375000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0985
_diffrn_reflns_av_unetI/netI     0.0852
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            25360
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.537
_diffrn_reflns_theta_min         2.044
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.110
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52786
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.57a (Rigaku Oxford Diffraction, 2023)
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    1.178
_exptl_crystal_description       prism
_exptl_crystal_F_000             524
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.398
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         6676
_refine_ls_number_restraints     625
_refine_ls_restrained_S_all      0.970
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0686P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1231
_refine_ls_wR_factor_ref         0.1258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4382
_reflns_number_total             6676
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 1.5790\% 
around [0.51 0.68 -0.52] (reciprocal) or [0.58 0.56 -0.59] (direct)
;
_cod_data_source_file            d3cc00442b2.cif
_cod_data_source_block           20221216hamadan_twin1_hklf4
_cod_original_cell_volume        1361.51(5)
_cod_database_code               7131804
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.979
_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. Restrained distances
 Si1-O1 \\sim Si1-O1A
 with sigma of 0.02
 O1-C2A \\sim O1A-C2A
 with sigma of 0.02
 O1-C18A \\sim O1A-C18A
 with sigma of 0.02
 O1-C11 \\sim O1A-C11
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C9A \\sim C17A \\sim C13A \\sim C8A \\sim C18A \\sim C7A \\sim C16A \\sim C6A
\\sim C20A \\sim C10A \\sim C12A \\sim C5A \\sim C14A \\sim C1A \\sim C15A
\\sim C2A \\sim C21A \\sim C3A \\sim C19A \\sim C4A \\sim O1A \\sim C11A:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
O1 \\sim C17 \\sim C10 \\sim C18 \\sim C21 \\sim C13 \\sim C14 \\sim C12 \\sim
C8 \\sim C11 \\sim C15 \\sim C2 \\sim C6 \\sim C1 \\sim C3 \\sim C19 \\sim C4
\\sim C9 \\sim C16 \\sim C20 \\sim C7 \\sim C5: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C19A) = Uanis(C20A) = Uanis(C21A)
4. Rigid body (RIGU) restrains
 O1, C18, C13, C12, C11, C2, C1, C19, C9, C20, C5, C15, C10, C6, C14, C3, C17,
 C4, C8, C16, C21, C7, C9A, C8A, C7A, C6A, C10A, C5A, C1A, C2A, C3A, C4A, C11A,
 C12A, C13A, C14A, C16A, C15A, C17A, C21A, C20A, C19A, C18A, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(C10A)=
 Sof(C9A)=Sof(H9A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=
 Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C17A)=Sof(H17A)=Sof(C21A)=
 Sof(H21F)=Sof(H21E)=Sof(H21D)=Sof(C20A)=Sof(H20D)=Sof(H20C)=Sof(C19A)=
 Sof(H19C)=Sof(H19D)=Sof(C18A)=Sof(H18A)=Sof(O1A)=1-FVAR(1)
 Sof(O1)=Sof(C18)=Sof(H18)=Sof(C13)=Sof(H13)=Sof(C12)=Sof(C11)=Sof(H11)=
 Sof(C2)=Sof(C1)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C9)=Sof(H9)=Sof(C20)=
 Sof(H20A)=Sof(H20B)=Sof(C5)=Sof(C15)=Sof(H15)=Sof(C10)=Sof(C6)=Sof(H6)=
 Sof(C14)=Sof(H14)=Sof(C3)=Sof(H3)=Sof(C17)=Sof(H17)=Sof(C4)=Sof(H4)=Sof(C8)=
 Sof(H8)=Sof(C16)=Sof(H16)=Sof(C21)=Sof(H21B)=Sof(H21A)=Sof(H21C)=Sof(C7)=
 Sof(H7)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C28(H28), C11(H11), C22(H22), C11A(H11A), C18A(H18A)
6.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C33(H33A,H33B), C27(H27A,H27B), C19(H19A,H19B), C29(H29A,
 H29B), C20(H20A,H20B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
 C31(H31A,H31B), C30(H30A,H30B), C32(H32A,H32B), C20A(H20D,H20C), C19A(H19C,
 H19D)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C9(H9), C15(H15), C6(H6), C14(H14), C3(H3), C17(H17), C4(H4),
 C8(H8), C16(H16), C7(H7), C3A(H3A), C4A(H4A), C9A(H9A), C8A(H8A), C7A(H7A),
 C6A(H6A), C13A(H13A), C14A(H14A), C16A(H16A), C15A(H15A), C17A(H17A)
6.d Naphthalene refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C10A,C9A,C8A,C7A,C6A)
6.e Idealised Me refined as rotating group:
 C21(H21B,H21A,H21C), C21A(H21F,H21E,H21D)
;
_shelx_res_checksum              71202
_shelx_hkl_checksum              6768
_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 1.657
_oxdiff_exptl_absorpt_empirical_full_min 0.557
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2