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_4128366
_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_absolute_configuration ad
_chemical_formula_moiety         'C21 H26 B Br2 N O2'
_chemical_formula_sum            'C21 H26 B Br2 N O2'
_chemical_formula_weight         495.06
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   18.5092(2)
_cell_length_b                   18.5092(2)
_cell_length_c                   12.71340(10)
_cell_measurement_reflns_used    34933
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.4660
_cell_measurement_theta_min      4.4040
_cell_volume                     3771.96(6)
_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 0.986
_diffrn_measured_fraction_theta_max 0.986
_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    -32.00   5.00   1.00    1.00    --    0.00  82.00  30.00   37
  2  \w    -52.00 -26.00   1.00    1.00    --    0.00 -38.00  30.00   26
  3  \w     21.00  89.00   1.00    1.00    --    0.00  77.00 150.00   68
  4  \w    -19.00  21.00   1.00    1.00    --    0.00  38.00 -60.00   40
  5  \w    -23.00  77.00   1.00    1.00    --    0.00  57.00 120.00  100
  6  \w     31.00  76.00   1.00    1.00    --    0.00  38.00 -60.00   45
  7  \w     -6.00  19.00   1.00    1.00    --    0.00 -26.00  97.84   25
  8  \w    -81.00 -55.00   1.00    1.00    --    0.00 -38.00  30.00   26
  9  \w    -17.00  28.00   1.00    1.00    --    0.00  38.00-120.00   45
 10  \w     -8.00  30.00   1.00    1.00    --    0.00  57.00   0.00   38
 11  \w    -66.00 -40.00   1.00    1.00    --    0.00 -26.00  97.84   26
 12  \w    -13.00  89.00   1.00    1.00    --    0.00  38.00   0.00  102
 13  \w     41.00  87.00   1.00    1.00    --    0.00  38.00-120.00   46
 14  \w    -30.00  12.00   1.00    1.00    --    0.00  77.00 150.00   42
 15  \w     18.00  55.00   1.00    1.00    --    0.00  82.00  30.00   37
 16  \w     56.00  88.00   1.00    1.00    --    0.00  57.00   0.00   32
 17  \w    -21.00  19.00   1.00    1.00    --    0.00 -38.00  30.00   40
 18  \w     67.00  93.00   1.00    2.00    --   95.80  71.00-101.82   26
 19  \w    141.00 173.00   1.00    2.00    --   95.80  77.00  83.31   32
 20  \w     71.00  96.00   1.00    2.00    --   95.80  59.00  31.65   25
 21  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  83.31   26
 22  \w     63.00  94.00   1.00    2.00    --   95.80  82.00  30.00   31
 23  \w     66.00 128.00   1.00    2.00    --   95.80 -82.00 -60.00   62
 24  \w     98.00 185.00   1.00    2.00    --   95.80  77.00 143.02   87
 25  \w    153.00 179.00   1.00    2.00    --   95.80  82.00  30.00   26
 26  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -30.00   26
 27  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  60.00   26
 28  \w     75.00 107.00   1.00    2.00    --   95.80  45.00   0.00   32
 29  \w     64.00 127.00   1.00    2.00    --   95.80 -82.00-180.00   63
 30  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 120.00   25
 31  \w     74.00 184.00   1.00    2.00    --   95.80  51.00-127.17  110
 32  \w     72.00 137.00   1.00    2.00    --   95.80  57.00 128.18   65
 33  \w     21.00  61.00   1.00    2.00    --   95.80 -82.00 -60.00   40
 34  \w     66.00  93.00   1.00    2.00    --   95.80  75.00 -34.00   27
 35  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 143.02   25
 36  \w     68.00 100.00   1.00    2.00    --   95.80  70.00  82.84   32
 37  \w     63.00  88.00   1.00    2.00    --   95.80  82.00-150.00   25
 38  \w    115.00 185.00   1.00    2.00    --   95.80  79.00 -18.99   70
 39  \w    131.00 185.00   1.00    2.00    --   95.80  59.00 -76.87   54
 40  \w     69.00 184.00   1.00    2.00    --   95.80  65.00-106.12  115
 41  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  90.00   26
 42  \w     94.00 185.00   1.00    2.00    --   95.80  82.00  90.00   91
 43  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  30.00   25
 44  \w     52.00  78.00   1.00    2.00    --   95.80 -82.00  90.00   26
 45  \w     92.00 128.00   1.00    2.00    --   95.80 -82.00  90.00   36
 46  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 120.00   25
 47  \w    102.00 185.00   1.00    2.00    --   95.80  82.00 120.00   83
 48  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -60.00   26
 49  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 150.00   25
 50  \w     63.00  88.00   1.00    2.00    --   95.80  82.00   0.00   25
 51  \w      6.00 126.00   1.00    2.00    --   95.80 -82.00-120.00  120
 52  \w     75.00 150.00   1.00    2.00    --   95.80  45.00  90.00   75
 53  \w     64.00  94.00   1.00    2.00    --   95.80  79.00 -18.99   30
 54  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -90.00   25
 55  \w    143.00 182.00   1.00    2.00    --   95.80  82.00 -90.00   39
 56  \w     63.00  88.00   1.00    2.00    --   95.80  82.00 -90.00   25
 57  \w    160.00 185.00   1.00    2.00    --   95.80  74.00 -62.73   25
 58  \w     72.00 109.00   1.00    2.00    --   95.80  59.00 -76.87   37
 59  \w     63.00  91.00   1.00    2.00    --   95.80  82.00-180.00   28
 60  \w     71.00 151.00   1.00    2.00    --   95.80  61.00 -60.00   80
 61  \w    159.00 185.00   1.00    2.00    --   95.80  61.00 -60.00   26
 62  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-180.00   25
 63  \w     65.00  90.00   1.00    2.00    --   95.80  77.00   0.00   25
 64  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  60.00   25
 65  \w     66.00  91.00   1.00    2.00    --   95.80  74.00 -62.73   25
 66  \w    121.00 159.00   1.00    2.00    --   95.80  45.00  60.00   38
 67  \w     75.00 103.00   1.00    2.00    --   95.80  45.00  60.00   28
 68  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 150.00   25
 69  \w     65.00 102.00   1.00    2.00    --   95.80  77.00 -60.00   37
 70  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-120.00   25
 71  \w     70.00 185.00   1.00    2.00    --   95.80  63.00-167.08  115
 72  \w     71.00  96.00   1.00    2.00    --   95.80  61.00-180.00   25
 73  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -30.00   26
 74  \w    107.00 183.00   1.00    2.00    --   95.80  82.00 -30.00   76
 75  \w     57.00 124.00   1.00    2.00    --   95.80 -82.00  30.00   67
 76  \w     71.00 117.00   1.00    2.00    --   95.80  61.00-120.00   46
 77  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-150.00   25
 78  \w      6.00 118.00   1.00    2.00    --   95.80 -82.00  60.00  112
 79  \w    106.00 171.00   1.00    2.00    --   95.80  59.00  31.65   65
 80  \w     75.00 102.00   1.00    2.00    --   95.80  45.00  30.00   27
 81  \w    159.00 185.00   1.00    2.00    --   95.80  57.00 128.18   26
;
_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      0.0160704000
_diffrn_orient_matrix_UB_12      0.0861851000
_diffrn_orient_matrix_UB_13      0.0363846000
_diffrn_orient_matrix_UB_21      0.0922572000
_diffrn_orient_matrix_UB_22      0.0274759000
_diffrn_orient_matrix_UB_23      0.0202704000
_diffrn_orient_matrix_UB_31      0.0215884000
_diffrn_orient_matrix_UB_32      0.0324643000
_diffrn_orient_matrix_UB_33      -0.1138258000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0933
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            96929
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         4.439
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.188
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29007
_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    1.308
_exptl_crystal_description       block
_exptl_crystal_F_000             1500
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 1723 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4446
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0488
_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^)+(0.1040P)^2^+0.4760P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1487
_refine_ls_wR_factor_ref         0.1518
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                4126
_reflns_number_total             4446
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13756_si_003.cif
_cod_data_source_block           exp_347
_cod_original_cell_volume        3771.96(9)
_cod_database_code               4128366
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.339
_shelx_estimated_absorpt_t_min   0.272
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 H18C-H20A
 2 with sigma of 0.01
3. Rigid bond restraints
 C16, C18, C19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C20, C21, C17
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C19 \\sim C16 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
C17 \\sim C20 \\sim C21: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
5.a Ternary CH refined with riding coordinates:
 C13(H13)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              948
_shelx_hkl_checksum              10555
_shelx_fab_checksum              47848
_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 2.323
_oxdiff_exptl_absorpt_empirical_full_min 0.501