Multiligand-enabled, copper-catalyzed Hiyama coupling of arylsilanes with unactivated secondary alkyl halides: reaction development and mechanistic insights.
Zhou, Jiajing; Zhang, Zhiqiang; Cao, Yan; Xie, Weilong; Chemical science 16 (2025) 5109–5117; doi:10.1039/d4sc07441f

data_1573846
_publ_section_title
;
 Multiligand-enabled, copper-catalyzed Hiyama coupling of arylsilanes with
 unactivated secondary alkyl halides: reaction development and mechanistic
 insights.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              5109
_journal_page_last               5117
_journal_paper_doi               10.1039/d4sc07441f
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C43 H52 Cu N4, 2(C7 H8), Br'
_chemical_formula_sum            'C57 H68 Br Cu N4'
_chemical_formula_weight         952.60
_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
_audit_creation_date             2024-05-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-06-09 deposited with the CCDC.	2025-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                90.934(7)
_cell_angle_beta                 111.881(7)
_cell_angle_gamma                110.488(5)
_cell_formula_units_Z            2
_cell_length_a                   12.3872(19)
_cell_length_b                   15.6834(19)
_cell_length_c                   16.433(3)
_cell_measurement_reflns_used    9817
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      25.322
_cell_measurement_theta_min      2.618
_cell_volume                     2735.3(8)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      180.00
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-III CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1169
_diffrn_reflns_av_unetI/netI     0.0641
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            77805
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.309
_diffrn_reflns_theta_min         2.612
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.167
_exptl_absorpt_correction_T_max  0.7279
_exptl_absorpt_correction_T_min  0.6299
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1542 before and 0.1118 after correction.
The Ratio of minimum to maximum transmission is 0.8654.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.157
_exptl_crystal_description       block
_exptl_crystal_F_000             1004
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.777
_refine_diff_density_min         -1.163
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         9776
_refine_ls_number_restraints     331
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0830
_refine_ls_R_factor_gt           0.0713
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1546P)^2^+0.5179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2151
_refine_ls_wR_factor_ref         0.2258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7748
_reflns_number_total             9776
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07441f2.cif
_cod_data_source_block           mo_zjj240530a_1_0m_a
_cod_depositor_comments          'Adding full bibliography for 1573846.cif.'
_cod_original_cell_volume        2735.2(7)
_cod_database_code               1573846
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.892
_shelx_estimated_absorpt_t_min   0.844
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C3
 1.51 with sigma of 0.02
 C3-C4 = C3-C8 = C5-C6
 1.39 with sigma of 0.02
 C4-C5 = C6-C7 = C7-C8
 1.38 with sigma of 0.02
 C3-C5
 2.42 with sigma of 0.04
 C4-C6
 2.39 with sigma of 0.04
 C3-C7
 2.41 with sigma of 0.04
 C5-C7 = C6-C8
 2.4 with sigma of 0.04
 C2-C4 = C2-C8
 2.52 with sigma of 0.04
 C3-C4 \\sim C4-C5 \\sim C5-C6 \\sim C6-C7 \\sim C7-C8 \\sim C8-C3
 with sigma of 0.02
 C3-C7 \\sim C3-C5 \\sim C8-C6 \\sim C4-C8 \\sim C5-C7 \\sim C4-C6
 with sigma of 0.04
 C2-C8 \\sim C2-C4
 with sigma of 0.04
3. Restrained planarity
 C2, C3, C4, C5, C6, C7, C8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C3 \\sim C2 \\sim C4 \\sim C8 \\sim C2A \\sim C4A \\sim C8A \\sim C5 \\sim C7
\\sim C5A \\sim C7A \\sim C6 \\sim C6A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 C2A, C3, C4A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=
 Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4A)=1-FVAR(1)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=
 Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C00K(H00K), C00N(H00N), C00O(H00O), C00Q(H00Q)
7.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C009(H009), C00G(H00G), C00J(H00J), C00L(H00L), C00R(H00R),
 C00S(H00S), C00U(H00U), C00W(H00W), C00X(H00X), C00Z(H00Z), C012(H012),
 C013(H013), C01A(H1), C01D(H2), C01G(H3), C01J(H9), C4(H4), C5(H5), C6(H6),
 C7(H7), C8(H8), C8A(H8A), C7A(H7A), C6A(H6A), C5A(H5A), C4A(H4A)
7.c Fitted hexagon refined as free rotating group:
 C8A(C7A,C6A,C5A,C4A,C3)
7.d Idealised Me refined as rotating group:
 C00V(H00A,H00B,H00C), C014(H01A,H01B,H01C), C015(H01D,H01E,H01F), C016(H01G,
 H01H,H01I), C017(H01J,H01K,H01L), C018(H01M,H01N,H01O), C019(H01P,H01Q,H01R),
 C01B(H01S,H01T,H01U), C01C(H01V,H01W,H01X), C01E(H01Y,H,HA), C01F(H01Z,HB,HC),
 C01I(H01,HD,HE), C01N(H10,HF,HG), C2(H2A,H2B,H2C), C2A(H2AA,H2AB,H2AC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              94706
_shelx_fab_checksum              23857
_olex2_submission_special_instructions 'No special instructions were received'