Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes.
Yang, Liang-Liang; Evans, Declan; Xu, Bin; Li, Wen-Tao; Li, Mao-Lin; Zhu, Shou-Fei; Houk, K. N.; Zhou, Qi-Lin; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c04725

data_4135102
_publ_section_title
;
 Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by
 Electronic Properties of the Carbenes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c04725
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H21 N O2 Si'
_chemical_formula_sum            'C23 H21 N O2 Si'
_chemical_formula_weight         371.50
_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     direct
_audit_creation_date             2018-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 90.60(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.952(2)
_cell_length_b                   19.926(4)
_cell_length_c                   10.453(2)
_cell_measurement_reflns_used    5199
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      28.5741
_cell_measurement_theta_min      2.0441
_cell_volume                     2072.8(7)
_computing_cell_refinement       crystalclear
_computing_data_collection       crystalclear
_computing_data_reduction        crystalclear
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      113.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Rigaku Saturn 70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0802
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            16192
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.019
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_min         2.046
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.130
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7170
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   crystalclear
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       prism
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.700
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Flack x determined using 1889 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(11)
_refine_ls_extinction_coef       0.027(5)
_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   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         7292
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0912
_refine_ls_R_factor_gt           0.0763
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1184P)^2^+0.0900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1955
_refine_ls_wR_factor_ref         0.2095
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                5842
_reflns_number_total             7292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04725_si_003.cif
_cod_data_source_block           shelxl
_cod_original_cell_volume        2072.7(7)
_cod_database_code               4135102
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.975
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C24(H24)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27),
  C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C)
;
_shelx_res_checksum              72455
_shelx_hkl_checksum              52059
_olex2_submission_special_instructions 'No special instructions were received'