Rh-catalyzed enantioselective hydrosilylation of unactivated alkenes.
Wu, Yichen; Qian, Hao-Yang; Zhang, Heng; Zou, Jian-Ye; Wu, Qing-Yan; Nie, Xiao-Xue; Zheng, Long; Peng, Qian; Wang, Peng; Chemical science 16 (2025) 12594–12602; doi:10.1039/d5sc02711j

data_1574803
_publ_section_title
;
 Rh-catalyzed enantioselective hydrosilylation of unactivated alkenes.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              12594
_journal_page_last               12602
_journal_paper_doi               10.1039/d5sc02711j
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C26 H27 N O2 Si'
_chemical_formula_sum            'C26 H27 N O2 Si'
_chemical_formula_weight         413.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.139(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9119(10)
_cell_length_b                   7.9060(7)
_cell_length_c                   22.6326(18)
_cell_measurement_reflns_used    9963
_cell_measurement_temperature    173.00
_cell_measurement_theta_max      54.475
_cell_measurement_theta_min      3.128
_cell_volume                     2230.2(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      173.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0791
_diffrn_reflns_av_unetI/netI     0.0793
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            36515
_diffrn_reflns_point_group_measured_fraction_full 0.955
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.115
_diffrn_reflns_theta_min         3.085
_diffrn_source_current           2.57
_diffrn_source_power             0.17933459999999998
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.708
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.5413
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1387 before and 0.0885 after correction.
The Ratio of minimum to maximum transmission is 0.7210.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.992
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Flack x determined using 1735 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.12(3)
_refine_ls_extinction_coef       0.0038(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     546
_refine_ls_number_reflns         8087
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1396
_refine_ls_R_factor_gt           0.1022
_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^)+(0.1507P)^2^+5.6434P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2663
_refine_ls_wR_factor_ref         0.2951
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.906
_reflns_Friedel_fraction_max     0.892
_reflns_number_gt                5780
_reflns_number_total             8087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02711j2.cif
_cod_data_source_block           mj24004_0m
_cod_depositor_comments          'Adding full bibliography for 1574803.cif.'
_cod_database_code               1574803
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.889
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All Si(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 Si1(H1), Si1A(H1AA)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C1A(H1AB,H1AC), C2A(H2AA,
 H2AB), C3A(H3AA,H3AB), C4A(H4AA,H4AB)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16), C17(H17), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C7A(H7A), C8A(H8A), C9A(H9A),
 C10A(H10A), C15A(H15A), C16A(H16A), C17A(H17A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A), C26A(H26A)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C19A(H19D,H19E,H19F), C20A(H20D,
 H20E,H20F)
;
_shelx_res_checksum              93740
_olex2_submission_special_instructions 'No special instructions were received'