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_4128368
_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         'C15 H17 N O'
_chemical_formula_sum            'C15 H17 N O'
_chemical_formula_weight         227.29
_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             2018-05-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.4113(2)
_cell_length_b                   9.5630(2)
_cell_length_c                   18.3570(5)
_cell_measurement_reflns_used    9145
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.8690
_cell_measurement_theta_min      4.8250
_cell_volume                     1301.04(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 0.990
_diffrn_measured_fraction_theta_max 0.990
_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     28.00  88.00   1.00    4.00    --    0.00  38.00-120.00   60
  2  \w    -19.00  87.00   1.00    4.00    --    0.00  38.00-180.00  106
  3  \w     14.00  65.00   1.00    4.00    --    0.00  77.00 -90.00   51
  4  \w     17.00  49.00   1.00    4.00    --    0.00  57.00  90.00   32
  5  \w    -21.00  32.00   1.00    4.00    --    0.00  57.00 -30.00   53
  6  \w     -5.00  23.00   1.00    4.00    --    0.00  38.00-120.00   28
  7  \w     11.00  63.00   1.00    4.00    --    0.00  77.00  30.00   52
  8  \w    -27.00   7.00   1.00    4.00    --    0.00  77.00  30.00   34
  9  \w     55.00  87.00   1.00    4.00    --    0.00  57.00  90.00   32
 10  \w    -20.00   5.00   1.00    4.00    --    0.00  57.00  90.00   25
 11  \w    -30.00  -1.00   1.00    4.00    --    0.00  77.00 -90.00   29
 12  \w     36.00  84.00   1.00    4.00    --    0.00  57.00 -30.00   48
 13  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-150.00   25
 14  \w     65.00  91.00   1.00    2.00    --   95.80  77.00-120.00   26
 15  \w     68.00  94.00   1.00    2.00    --   95.80  68.00-161.04   26
 16  \w     88.00 128.00   1.00    2.00    --   95.80 -82.00 120.00   40
 17  \w     27.00  75.00   1.00    2.00    --   95.80 -82.00 120.00   48
 18  \w    113.00 185.00   1.00    2.00    --   95.80  72.00 -96.68   72
 19  \w     66.00  91.00   1.00    2.00    --   95.80  74.00 -32.53   25
 20  \w     63.00  96.00   1.00    2.00    --   95.80  82.00 -90.00   33
 21  \w     72.00 167.00   1.00    2.00    --   95.80  61.00   0.00   95
 22  \w     65.00  90.00   1.00    2.00    --   95.80  77.00  60.00   25
 23  \w     73.00 100.00   1.00    2.00    --   95.80  61.00-180.00   27
 24  \w     44.00 128.00   1.00    2.00    --   95.80 -82.00  60.00   84
 25  \w     76.00 103.00   1.00    2.00    --   95.80  45.00 -90.00   27
 26  \w     12.00 120.00   1.00    2.00    --   95.80 -61.00 -60.00  108
 27  \w     67.00  93.00   1.00    2.00    --   95.80  72.00  33.88   26
 28  \w     65.00  90.00   1.00    2.00    --   95.80  77.00   0.00   25
 29  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -30.00   26
 30  \w     71.00 112.00   1.00    2.00    --   95.80  61.00  60.00   41
 31  \w     76.00 169.00   1.00    2.00    --   95.80  45.00-180.00   93
 32  \w     67.00  92.00   1.00    2.00    --   95.80  72.00 -96.68   25
 33  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 120.00   26
 34  \w     76.00 154.00   1.00    2.00    --   95.80  45.00 -30.00   78
 35  \w     73.00 110.00   1.00    2.00    --   95.80  61.00  90.00   37
 36  \w    142.00 185.00   1.00    2.00    --   95.80  77.00 -60.00   43
 37  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-180.00   25
 38  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -60.00   26
 39  \w     64.00 183.00   1.00    2.00    --   95.80  80.00   8.23  119
 40  \w      7.00 118.00   1.00    2.00    --   95.80 -82.00 -60.00  111
 41  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -60.00   25
 42  \w    121.00 181.00   1.00    2.00    --   95.80  72.00  33.88   60
 43  \w     63.00  94.00   1.00    2.00    --   95.80  82.00-150.00   31
 44  \w    122.00 184.00   1.00    2.00    --   95.80  82.00-150.00   62
 45  \w     76.00 101.00   1.00    2.00    --   95.80  45.00-120.00   25
 46  \w     71.00  97.00   1.00    2.00    --   95.80  61.00 -90.00   26
 47  \w     63.00  89.00   1.00    2.00    --   95.80  82.00  30.00   26
 48  \w     63.00  88.00   1.00    2.00    --   95.80  82.00  90.00   25
 49  \w     63.00 107.00   1.00    2.00    --   95.80 -82.00-150.00   44
 50  \w     76.00 128.00   1.00    2.00    --   95.80  30.00 -90.00   52
 51  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 150.00   25
 52  \w     80.00 133.00   1.00    2.00    --   95.80  45.00 -60.00   53
 53  \w    129.00 155.00   1.00    2.00    --   95.80  61.00  60.00   26
 54  \w     65.00  91.00   1.00    2.00    --   95.80  82.00 120.00   26
 55  \w    127.00 175.00   1.00    2.00    --   95.80  68.00-161.04   48
 56  \w     96.00 172.00   1.00    2.00    --   95.80  74.00 -32.53   76
 57  \w    149.00 176.00   1.00    2.00    --   95.80  62.00 103.69   27
 58  \w     77.00 182.00   1.00    2.00    --   95.80  45.00 150.00  105
 59  \w     70.00 127.00   1.00    2.00    --   95.80  62.00 103.69   57
;
_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      -0.0285482000
_diffrn_orient_matrix_UB_12      0.1091774000
_diffrn_orient_matrix_UB_13      -0.0606044000
_diffrn_orient_matrix_UB_21      -0.1038477000
_diffrn_orient_matrix_UB_22      0.0937882000
_diffrn_orient_matrix_UB_23      0.0538359000
_diffrn_orient_matrix_UB_31      0.1777909000
_diffrn_orient_matrix_UB_32      0.0723539000
_diffrn_orient_matrix_UB_33      0.0217224000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0979
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25304
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.019
_diffrn_reflns_theta_max         67.019
_diffrn_reflns_theta_min         4.818
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.565
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76809
_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    1.160
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.100
_refine_diff_density_min         -0.094
_refine_diff_density_rms         0.021
_refine_ls_abs_structure_details
;
 Flack x determined using 736 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_coef       0.0058(9)
_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   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     158
_refine_ls_number_reflns         2292
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0509P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0894
_reflns_Friedel_coverage         0.694
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                2008
_reflns_number_total             2292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b13756_si_002.cif
_cod_data_source_block           exp_343
_cod_database_code               4128368
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.93
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C2(H2), C12(H12), C9(H9), C4(H4), C3(H3), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              49551
_shelx_hkl_checksum              39560
_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 3.071
_oxdiff_exptl_absorpt_empirical_full_min 0.284