Synthesis of Silicon-Stereogenic Silanols Involving Iridium-Catalyzed Enantioselective C‒H Silylation Leading to a New Ligand Scaffold
Zhang, Hongpeng; Zhao, Dongbing; ACS Catalysis  (2021) 10748–10753; doi:10.1021/acscatal.1c03112

data_4518970
_publ_section_title
;
 Synthesis of Silicon-Stereogenic Silanols Involving Iridium-Catalyzed
 Enantioselective C--H Silylation Leading to a New Ligand Scaffold
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10748
_journal_page_last               10753
_journal_paper_doi               10.1021/acscatal.1c03112
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H28 N O2 P Si'
_chemical_formula_sum            'C20 H28 N O2 P Si'
_chemical_formula_weight         373.49
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                81.234(4)
_cell_angle_beta                 84.074(3)
_cell_angle_gamma                68.141(4)
_cell_formula_units_Z            2
_cell_length_a                   7.2482(3)
_cell_length_b                   9.4977(4)
_cell_length_c                   16.2110(7)
_cell_measurement_reflns_used    10299
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      32.9240
_cell_measurement_theta_min      2.4280
_cell_volume                     1022.33(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrystalClear (Rigaku, 2008)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      113.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -115.00  65.00   1.00    1.00    --  -25.00  45.00   0.00  180
  2  \w   -115.00  65.00   1.00    1.00    --  -25.00  45.00  90.00  180
  3  \w   -115.00  65.00   1.00    1.00    --  -25.00  45.00 180.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Saturn 70'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0267221000
_diffrn_orient_matrix_UB_12      -0.0306659000
_diffrn_orient_matrix_UB_13      0.0416427000
_diffrn_orient_matrix_UB_21      -0.1018460000
_diffrn_orient_matrix_UB_22      0.0169293000
_diffrn_orient_matrix_UB_23      0.0126185000
_diffrn_orient_matrix_UB_31      0.0076783000
_diffrn_orient_matrix_UB_32      -0.0731291000
_diffrn_orient_matrix_UB_33      -0.0084744000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            12866
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.699
_diffrn_reflns_theta_min         2.328
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.206
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.413
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 3707 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_coef       0.016(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     462
_refine_ls_number_reflns         9304
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0491P)^2^+0.0448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0852
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.840
_reflns_Friedel_fraction_max     0.773
_reflns_number_gt                8975
_reflns_number_total             9304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03112_si_003.cif
_cod_data_source_block           r20210311a
_cod_database_code               4518970
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 88.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.91
_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:
 C1(H1A,H1B), C3(H3A,H3B), C21(H21A,H21B), C23(H23A,H23B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34),
  C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.379
_oxdiff_exptl_absorpt_empirical_full_min 0.711