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_7131802
_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         'C30 H39 N O2 S Si'
_chemical_formula_sum            'C30 H39 N O2 S Si'
_chemical_formula_weight         505.77
_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     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                90
_cell_angle_beta                 111.762(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8834(16)
_cell_length_b                   10.0790(6)
_cell_length_c                   15.7187(14)
_cell_measurement_reflns_used    17282
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      28.2280
_cell_measurement_theta_min      2.3210
_cell_volume                     2778.5(4)
_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 0.999
_diffrn_measured_fraction_theta_max 0.929
_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    -86.00  78.00   0.50   20.00    --  -12.00  45.00 -20.00  328
  2  \w    -78.00  60.00   0.50   20.00    --  -12.00  45.00 228.00  276
  3  \w    -73.00  60.00   0.50   20.00    --  -12.00  45.00 122.00  266
  4  \w    -73.00  60.00   0.50   20.00    --  -12.00  45.00  51.00  266
  5  \w      9.50  56.50   0.50   20.00    --  -12.00  45.00 300.00   94
  6  \w     12.00  69.50   0.50   20.00    --  -12.00  45.00 157.00  115
;
_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      0.0353690000
_diffrn_orient_matrix_UB_12      -0.0341117000
_diffrn_orient_matrix_UB_13      0.0139273000
_diffrn_orient_matrix_UB_21      -0.0188002000
_diffrn_orient_matrix_UB_22      -0.0571090000
_diffrn_orient_matrix_UB_23      -0.0243665000
_diffrn_orient_matrix_UB_31      0.0055223000
_diffrn_orient_matrix_UB_32      0.0230301000
_diffrn_orient_matrix_UB_33      -0.0397031000
_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  0.0580
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            45872
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.676
_diffrn_reflns_theta_min         2.331
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.187
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63788
_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    1.209
_exptl_crystal_description       prism
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     465
_refine_ls_number_reflns         7294
_refine_ls_number_restraints     463
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0899
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0759P)^2^+1.5639P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1497
_refine_ls_wR_factor_ref         0.1651
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5140
_reflns_number_total             7294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00442b2.cif
_cod_data_source_block           20220126_hamada_autored
_cod_database_code               7131802
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.964
_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
 C24A-C19A = C24A-C23A = C23A-C22A = C22A-C21A = C21A-C20A = C20A-C19A
 1.54 with sigma of 0.01
 C23A-C19A = C24A-C20A
 2.54 with sigma of 0.01
 C21A-C23A = C22A-C24A
 2.54 with sigma of 0.01
 C19A-C21A = C20A-C22A
 2.54 with sigma of 0.01
 Si1-C19 \\sim Si1-C19A
 with sigma of 0.01
 C19-C20 \\sim C21-C20 \\sim C22-C21 \\sim C22-C23 \\sim C24-C23 \\sim C24-C19
 with sigma of 0.01
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 Si1-C25 \\sim Si1-C25A
 with sigma of 0.02
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C25-C30 \\sim C25A-C30A
 with sigma of 0.02
 C28-C27 \\sim C28A-C27A
 with sigma of 0.02
 C30-C29 \\sim C30A-C29A
 with sigma of 0.02
 C26-C30 \\sim C26A-C30A
 with sigma of 0.04
 Si1-C26 \\sim Si1-C26A
 with sigma of 0.04
 Si1-C30 \\sim Si1-C30A
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C25-C29 \\sim C25A-C29A
 with sigma of 0.04
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C19 \\sim C22 \\sim C20 \\sim C21 \\sim C24 \\sim C23 \\sim C22A \\sim C21A
\\sim C23A \\sim C20A \\sim C24A \\sim C19A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C25 \\sim C28 \\sim C26 \\sim C30 \\sim C27 \\sim C29 \\sim C25A \\sim C28A
\\sim C26A \\sim C30A \\sim C27A \\sim C29A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C19, C22, C20, C21, C24, C23, C22A, C21A, C23A, C20A, C24A, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17C)=
 Sof(H17D)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
 Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C23A)=
 Sof(H23C)=Sof(H23D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C24A)=Sof(H24C)=
 Sof(H24D)=Sof(C19A)=Sof(H19A)=1-FVAR(2)
 Sof(C19)=Sof(H19)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=FVAR(2)
 Sof(C25A)=Sof(H25A)=Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C26A)=Sof(H26C)=
 Sof(H26D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C27A)=Sof(H27C)=Sof(H27D)=
 Sof(C29A)=Sof(H29C)=Sof(H29D)=1-FVAR(3)
 Sof(C25)=Sof(H25)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C15(H15), C15A(H15A), C19(H19), C19A(H19A), C25A(H25A)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C26(H26A,H26B), C30(H30A,H30B), C27(H27A,H27B), C29(H29A,
 H29B), C17(H17A,H17B), C16(H16A,H16B), C16A(H16C,H16D), C17A(H17C,H17D),
 C22(H22A,H22B), C20(H20A,H20B), C21(H21A,H21B), C24(H24A,H24B), C23(H23A,H23B),
  C22A(H22C,H22D), C21A(H21C,H21D), C23A(H23C,H23D), C20A(H20C,H20D), C24A(H24C,
 H24D), C28A(H28C,H28D), C26A(H26C,H26D), C30A(H30C,H30D), C27A(H27C,H27D),
 C29A(H29C,H29D)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C4(H4), C8(H8), C14(H14), C10(H10), C3(H3), C13(H13), C12(H12),
 C11(H11)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C18A(H18D,H18E,H18F)
;
_shelx_res_checksum              35870
_shelx_hkl_checksum              66155
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.319
_oxdiff_exptl_absorpt_empirical_full_min 0.699