Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp<sup>2</sup>)-H Borylation of Diarylmethylamines.
Zou, Xiaoliang; Zhao, Haonan; Li, Yinwu; Gao, Qian; Ke, Zhuofeng; Senmiao Xu, ?; Journal of the American Chemical Society 141 (2019) 5334–5342; doi:10.1021/jacs.8b13756

data_4128367
_publ_section_title
;
 Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric
 C(sp<sup>2</sup>)-H Borylation of Diarylmethylamines.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5334
_journal_page_last               5342
_journal_paper_doi               10.1021/jacs.8b13756
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C38 H45 B Cl Ir N2 O Si'
_chemical_formula_sum            'C38 H45 B Cl Ir N2 O Si'
_chemical_formula_weight         812.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.23300(10)
_cell_length_b                   18.23640(10)
_cell_length_c                   19.01230(10)
_cell_measurement_reflns_used    37268
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.0810
_cell_measurement_theta_min      4.3010
_cell_volume                     4241.38(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_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    -16.00  29.00   1.00    1.00    --    0.00 -77.00 -60.00   45
  2  \w    -75.00 -49.00   1.00    1.00    --    0.00 -57.00  60.00   26
  3  \w    -50.00  14.00   1.00    1.00    --    0.00 -38.00  60.00   64
  4  \w    -13.00  82.00   1.00    1.00    --    0.00  38.00 -60.00   95
  5  \w    -75.00 -37.00   1.00    1.00    --    0.00 -77.00 -60.00   38
  6  \w    -48.00 -21.00   1.00    1.00    --    0.00 -38.00 -60.00   27
  7  \w    -54.00  18.00   1.00    1.00    --    0.00 -38.00 -30.00   72
  8  \w     47.00  89.00   1.00    1.00    --    0.00  57.00 -30.00   42
  9  \w     18.00  67.00   1.00    2.00    --   95.80 -82.00  90.00   49
 10  \w    117.00 183.00   1.00    2.00    --   95.80  15.00 -90.00   66
 11  \w     54.00 107.00   1.00    2.00    --   95.80 -82.00 150.00   53
 12  \w     88.00 127.00   1.00    2.00    --   95.80 -82.00   0.00   39
 13  \w     26.00 103.00   1.00    2.00    --   95.80 -82.00 -30.00   77
 14  \w     77.00 103.00   1.00    2.00    --   95.80 -82.00  90.00   26
 15  \w     76.00 144.00   1.00    2.00    --   95.80  30.00  90.00   68
 16  \w     68.00 114.00   1.00    2.00    --   95.80  15.00 -90.00   46
 17  \w     96.00 122.00   1.00    2.00    --   95.80 -82.00 -60.00   26
 18  \w     85.00 183.00   1.00    2.00    --   95.80  30.00 150.00   98
 19  \w      7.00  36.00   1.00    2.00    --   95.80 -82.00 -60.00   29
 20  \w     18.00 112.00   1.00    2.00    --   95.80 -30.00-150.00   94
 21  \w     23.00 128.00   1.00    2.00    --   95.80 -82.00  60.00  105
 22  \w     54.00 101.00   1.00    2.00    --   95.80 -82.00 -90.00   47
 23  \w    160.00 185.00   1.00    2.00    --   95.80  30.00  90.00   25
 24  \w     78.00 182.00   1.00    2.00    --   95.80  30.00-180.00  104
 25  \w     96.00 125.00   1.00    2.00    --   95.80 -82.00-180.00   29
 26  \w     15.00 127.00   1.00    2.00    --   95.80 -82.00-120.00  112
 27  \w     38.00 105.00   1.00    2.00    --   95.80 -61.00 150.00   67
 28  \w     33.00  78.00   1.00    2.00    --   95.80 -61.00 -30.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0275366000
_diffrn_orient_matrix_UB_12      -0.0746233000
_diffrn_orient_matrix_UB_13      -0.0335642000
_diffrn_orient_matrix_UB_21      -0.0084371000
_diffrn_orient_matrix_UB_22      -0.0369290000
_diffrn_orient_matrix_UB_23      0.0726487000
_diffrn_orient_matrix_UB_31      -0.1226507000
_diffrn_orient_matrix_UB_32      -0.0142021000
_diffrn_orient_matrix_UB_33      -0.0125754000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1573
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            46729
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         4.850
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.144
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25369
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.34
_refine_diff_density_max         1.683
_refine_diff_density_min         -1.624
_refine_diff_density_rms         0.156
_refine_ls_abs_structure_details
;
 Flack x determined using 3197 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(10)
_refine_ls_extinction_coef       0.00206(16)
_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   1.004
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         7525
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0861P)^2^+2.1295P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1115
_reflns_Friedel_coverage         0.794
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                7358
_reflns_number_total             7525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13756_si_001.cif
_cod_data_source_block           exp_263
_cod_database_code               4128367
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.195
_shelx_estimated_absorpt_t_min   0.158
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 C10, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C10 \\sim C11: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
Uanis(C5) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C4) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C8(H8), C20(H20), C34(H34)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33)
4.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C)
;
_shelx_res_checksum              31456
_shelx_hkl_checksum              12765
_shelx_fab_checksum              67243
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 4.206
_oxdiff_exptl_absorpt_empirical_full_min 0.420