Chelation-assisted multiple and relay C–H functionalization of unactivated aliphatic E-alkenes
Wang, Yini; Li, Xiaoli; Peng, Chengxing; Chen, Yu; Lu, Xi; Zhu, Yuhang; Yu, Peiyuan; Zhong, Guofu; Zhang, Jian; Chemical Science  (2025) –; doi:10.1039/D5SC07408H

data_1576232
_publ_section_title
;
 Chelation-assisted multiple and relay C--H functionalization of
 unactivated aliphatic E-alkenes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07408H
_journal_year                    2025
_chemical_formula_moiety         'C37 H63 N3 O Si2'
_chemical_formula_sum            'C37 H63 N3 O Si2'
_chemical_formula_weight         622.08
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-01-26 deposited with the CCDC.	2025-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.1747(7)
_cell_length_b                   21.3153(13)
_cell_length_c                   33.4672(19)
_cell_measurement_reflns_used    9007
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      60.569
_cell_measurement_theta_min      3.787
_cell_volume                     7971.6(8)
_computing_cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.14'
_computing_data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'zju Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0856
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            221069
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         61.045
_diffrn_reflns_theta_min         3.608
_diffrn_source_current           3.57
_diffrn_source_power             0.24957869999999996
_diffrn_source_voltage           69.91
_exptl_absorpt_coefficient_mu    0.659
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1338 before and 0.0731 after correction.
The Ratio of minimum to maximum transmission is 0.8963.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.037
_exptl_crystal_description       needle
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.373
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         9207
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.241
_refine_ls_R_factor_all          0.0910
_refine_ls_R_factor_gt           0.0713
_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^)+(0.0911P)^2^+6.5450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1847
_refine_ls_wR_factor_ref         0.1982
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7109
_reflns_number_total             9207
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07408h3.cif
_cod_data_source_block           240523_zc_30si
_cod_database_code               1576232
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.949
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C7-C8 \\sim C7-C8A
 with sigma of 0.02
 C21-C8 \\sim C21-C8A
 with sigma of 0.04
 C9-C8 \\sim C9-C8A
 with sigma of 0.02
 C32-C20 \\sim C32-C20A
 with sigma of 0.02
 C9-C20 \\sim C9-C20A
 with sigma of 0.04
 C21-C20 \\sim C21-C20A
 with sigma of 0.02
 C20-C8 \\sim C20A-C8A
 with sigma of 0.02
 C7-C20 \\sim C7-C20A
 with sigma of 0.04
 C32-C8 \\sim C32-C8A
 with sigma of 0.04
 Si2-C28 \\sim Si2-C28A
 with sigma of 0.04
 C26-C28 \\sim C26A-C28A
 with sigma of 0.02
 Si2-C27 \\sim Si2-C27A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.04
 Si2-C26 \\sim Si2-C26A
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A
 with sigma of 0.04
 C33-C34 \\sim C33-C34A
 with sigma of 0.02
 C35-C37 \\sim C35A-C37A
 with sigma of 0.04
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C33-C35 \\sim C33-C35A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36A
 with sigma of 0.02
 C36-C37 \\sim C36A-C37A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C7 \\sim C8 \\sim C8A \\sim C20 \\sim C20A: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
Si2 \\sim C26 \\sim C26A \\sim C27 \\sim C27A \\sim C28 \\sim C28A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C32 \\sim C33 \\sim C34 \\sim C34A \\sim C35 \\sim C35A \\sim C36 \\sim C36A
\\sim C37 \\sim C37A: within 2A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 2A
Uanis(C20) = Uanis(C20A)
Uanis(C8) = Uanis(C8A)
4. Others
 Sof(H7BC)=Sof(H7BD)=Sof(C8A)=Sof(C20A)=Sof(H32C)=Sof(H32D)=1-FVAR(1)
 Sof(H7AA)=Sof(H7AB)=Sof(C8)=Sof(C20)=Sof(H32A)=Sof(H32B)=FVAR(1)
 Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=
 Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(2)
 Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=
 Sof(H28B)=Sof(H28C)=FVAR(2)
 Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=
 Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=1-FVAR(3)
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(3)
 Fixed X: C8A(0.405479) C20A(0.294499)
 Fixed Y: C8A(0.24795) C20A(0.25572)
 Fixed Z: C8A(0.628541) C20A(0.61761)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C17(H17), C23(H23), C26(H26), C26A(H26A), C29(H29)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7AA,H7AB), C7(H7BC,H7BD), C32(H32A,H32B), C32(H32C,H32D),
 C33(H33A,H33B), C33(H33C,H33D), C34(H34A,H34B), C34A(H34C,H34D), C35(H35A,
 H35B), C35A(H35C,H35D), C36(H36A,H36B), C36A(H36C,H36D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), N3(H3), C3(H3A)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C27(H27A,H27B,H27C), C27A(H27D,H27E,H27F), C28(H28A,H28B,H28C),
 C28A(H28D,H28E,H28F), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C37(H37A,H37B,
 H37C), C37A(H37D,H37E,H37F)
;
_olex2_submission_special_instructions 'No special instructions were received'