Metal-free C(sp3)–Si activation enables regiocontrolled [4 + 2] cycloaddition to benzosilacycloethers
Gao, Liuzhou; Wen, Yan; Sun, Yan; Sun, Yuxin; Hu, Jingyi; Wang, Shenglong; Li, Zhenxing; Han, Ying; Wang, Yidong; Green Chemistry 27 (2025) 10242–10249; doi:10.1039/D5GC03044G

data_7250779
_publ_section_title
;
 Metal-free C(sp3)--Si activation enables regiocontrolled [4 + 2]
 cycloaddition to benzosilacycloethers
;
_journal_issue                   34
_journal_name_full               'Green Chemistry'
_journal_page_first              10242
_journal_page_last               10249
_journal_paper_doi               10.1039/D5GC03044G
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C26 H23 Cl O2 Si'
_chemical_formula_sum            'C26 H23 Cl O2 Si'
_chemical_formula_weight         430.98
_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             2025-02-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-04 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.477(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2217(13)
_cell_length_b                   25.507(3)
_cell_length_c                   9.3872(11)
_cell_measurement_reflns_used    3972
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      21.590
_cell_measurement_theta_min      2.272
_cell_volume                     2292.8(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0772
_diffrn_reflns_av_unetI/netI     0.1264
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19510
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.416
_diffrn_reflns_theta_min         1.597
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.238
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6746
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1567 before and 0.0540 after correction.
The Ratio of minimum to maximum transmission is 0.9048.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light white'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.278
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         5170
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.2032
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0458P)^2^+0.7370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1107
_refine_ls_wR_factor_ref         0.1433
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2175
_reflns_number_total             5170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc03044g2.cif
_cod_data_source_block           wyd20250224wy_0ma
_cod_depositor_comments          'Adding full bibliography for 7250779.cif.'
_cod_database_code               7250779
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.932
_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 Secondary CH2 refined with riding coordinates:
 C00B(H00A,H00B)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C008(H008), C00C(H00C), C00D(H00D), C00F(H00F), C00G(H00G),
 C00H(H00H), C00I(H00I), C00J(H00J), C00N(H00N), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00T(H00T), C00U(H00U)
2.c Idealised Me refined as rotating group:
 C00R(H00E,H00K,H00L), C00S(H00M,H00R,H00S)
;
_shelx_res_checksum              63616
_shelx_hkl_checksum              36925
_olex2_submission_special_instructions 'No special instructions were received'