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_7131805
_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         'C38 H43 N Si'
_chemical_formula_sum            'C38 H43 N Si'
_chemical_formula_weight         541.82
_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'
_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                 106.116(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.9951(8)
_cell_length_b                   8.0662(3)
_cell_length_c                   35.0695(12)
_cell_measurement_reflns_used    16358
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      25.3250
_cell_measurement_theta_min      2.4950
_cell_volume                     6249.2(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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   10.00    --  -12.00  45.00  51.00  360
  2  \w    -86.50  78.00   0.50   10.00    --  -12.00  45.00 193.00  329
  3  \w    -97.00  17.00   0.50   10.00    --  -12.00  45.00 264.00  228
;
_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      -0.0013717000
_diffrn_orient_matrix_UB_12      0.0035954000
_diffrn_orient_matrix_UB_13      -0.0204320000
_diffrn_orient_matrix_UB_21      0.0297110000
_diffrn_orient_matrix_UB_22      -0.0330293000
_diffrn_orient_matrix_UB_23      0.0043052000
_diffrn_orient_matrix_UB_31      -0.0121292000
_diffrn_orient_matrix_UB_32      -0.0814164000
_diffrn_orient_matrix_UB_33      -0.0026461000
_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  0.0788
_diffrn_reflns_av_unetI/netI     0.0751
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            59490
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.336
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77709
_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    1.152
_exptl_crystal_description       prism
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.589
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         11450
_refine_ls_number_restraints     432
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.1274
_refine_ls_R_factor_gt           0.0779
_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^)+(0.0160P)^2^+11.1274P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1526
_refine_ls_wR_factor_ref         0.1699
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7463
_reflns_number_total             11450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00442b2.cif
_cod_data_source_block           20221121hamada_autored
_cod_database_code               7131805
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C38 H43 N1 Si1'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 N2-C58A \\sim N2-C58
 with sigma of 0.01
 C57A-C58A \\sim C58-C57
 with sigma of 0.01
 Si2-C71A \\sim Si2-C71
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C76 \\sim C75 \\sim C75A \\sim C76A \\sim C71 \\sim C72 \\sim C71A \\sim C74
\\sim C73 \\sim C73A \\sim C74A \\sim C72A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C34 \\sim C33 \\sim C36 \\sim C38 \\sim C35 \\sim C37 \\sim C36A \\sim C37A
\\sim C38A \\sim C35A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C57 \\sim C58 \\sim C56 \\sim C56A \\sim C57A \\sim C58A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C40 \\sim C55A \\sim C56A \\sim C57A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C34, C33, C36, C38, C35, C37, C36A, C37A, C38A, C35A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H34C)=Sof(H34D)=Sof(H33A)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=
 Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C35A)=Sof(H35C)=
 Sof(H35D)=1-FVAR(1)
 Sof(H34A)=Sof(H34B)=Sof(H33)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C37)=Sof(H37A)=Sof(H37B)=FVAR(1)
 Sof(C56A)=Sof(H56C)=Sof(H56D)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(C58A)=
 Sof(H58C)=Sof(H58D)=Sof(C55A)=Sof(H55A)=1-FVAR(2)
 Sof(C55)=Sof(H55)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=FVAR(2)
 Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C73A)=Sof(H73C)=
 Sof(H73D)=Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=
 Sof(C76A)=Sof(H76C)=Sof(H76D)=1-FVAR(3)
 Sof(C71)=Sof(H71)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C75)=Sof(H75A)=Sof(H75B)=
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C17(H17), C49(H49), C11(H11), C33(H33), C33(H33A), C71(H71), C55(H55),
 C55A(H55A), C71A(H71A)
6.b Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C54(H54A,H54B), C18(H18A,H18B), C50(H50A,H50B), C51(H51A,
 H51B), C16(H16A,H16B), C19(H19A,H19B), C20(H20A,H20B), C53(H53A,H53B),
 C34(H34A,H34B), C34(H34C,H34D), C15(H15A,H15B), C14(H14A,H14B), C12(H12A,H12B),
  C13(H13A,H13B), C36(H36A,H36B), C38(H38A,H38B), C76(H76A,H76B), C35(H35A,
 H35B), C75(H75A,H75B), C37(H37A,H37B), C74(H74A,H74B), C57(H57A,H57B),
 C58(H58A,H58B), C72(H72A,H72B), C56(H56A,H56B), C73(H73A,H73B), C36A(H36C,
 H36D), C37A(H37C,H37D), C38A(H38C,H38D), C35A(H35C,H35D), C56A(H56C,H56D),
 C57A(H57C,H57D), C58A(H58C,H58D), C72A(H72C,H72D), C73A(H73C,H73D), C74A(H74C,
 H74D), C75A(H75C,H75D), C76A(H76C,H76D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C45(H45), C47(H47), C46(H46), C44(H44), C6(H6), C27(H27),
 C9(H9), C42(H42), C7(H7), C32(H32), C8(H8), C24(H24), C21(H21), C30(H30),
 C26(H26), C25(H25), C41(H41), C31(H31), C59(H59), C64(H64), C63(H63), C65(H65),
  C62(H62), C68(H68), C69(H69), C70(H70)
;
_shelx_res_checksum              86877
_shelx_hkl_checksum              69735
_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 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.775