Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C-H Arylation of Heteroarenes.
Nguyen, Qui-Hien; Guo, Shu-Min; Royal, Titouan; Baudoin, Olivier; Cramer, Nicolai; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b12299

data_4134060
_publ_section_title
;
 Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C-H
 Arylation of Heteroarenes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b12299
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C17 H19 N3 O'
_chemical_formula_sum            'C17 H19 N3 O'
_chemical_formula_weight         281.35
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 98.3391(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.0810(3)
_cell_length_b                   8.25102(13)
_cell_length_c                   19.9954(3)
_cell_measurement_reflns_used    19587
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4760
_cell_measurement_theta_min      3.4390
_cell_volume                     3114.75(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Mercury 4.2.0 (CCDC, 2019)'
_computing_publication_material  'CIFTab (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_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      2.00  27.00   1.00    3.00    --   38.00  88.00  10.71   25
  2  \w    -68.00  30.00   1.00    3.00    --  -40.91  57.00  30.00   98
  3  \w   -107.00 -18.00   1.00    3.00    --  -40.91 -38.00  30.00   89
  4  \w    -91.00 -13.00   1.00    3.00    --  -40.91 -57.00-150.00   78
  5  \w   -114.00 -18.00   1.00    3.00    --  -40.91 -38.00 -60.00   96
  6  \w     27.00  96.00   1.00    3.00    --   40.91-125.00-180.00   69
  7  \w      5.00  30.00   1.00    3.00    --   40.91  87.00  95.15   25
  8  \w     16.00  41.00   1.00    3.00    --   50.00  81.00 -72.36   25
  9  \w     16.00  41.00   1.00    3.00    --   50.00  81.00 101.36   25
 10  \w     16.00  41.00   1.00    3.00    --   50.00  81.00  -6.14   25
 11  \w     16.00  41.00   1.00    3.00    --   50.00  82.00-142.33   25
 12  \w     16.00  42.00   1.00    3.00    --   50.00  82.00 143.92   26
 13  \w     28.00  69.00   1.00    3.00    --   58.00  72.00  41.02   41
 14  \w     88.00 115.00   1.00    3.00    --   58.00  74.00 -98.12   27
 15  \w     33.00  60.00   1.00    3.00    --   58.00  74.00 -98.12   27
 16  \w     30.00  57.00   1.00    3.00    --   62.00  74.00 114.12   27
 17  \w    101.00 129.00   1.00    3.00    --   66.00  74.00 -57.56   28
 18  \w     36.00  61.00   1.00    3.00    --   66.00  74.00 -57.56   25
 19  \w     36.00  63.00   1.00    3.00    --   66.00  74.00 138.87   27
 20  \w     38.00  63.00   1.00    3.00    --   66.00  73.00 -33.32   25
 21  \w     41.00  67.00   1.00    3.00    --   70.00  64.00-160.38   26
 22  \w    104.00 145.00   1.00    3.00    --   70.00  73.00  56.60   41
 23  \w     98.00 145.00   1.00    3.00    --   70.00  74.00-134.73   47
 24  \w     40.00  69.00   1.00    3.00    --   70.00  68.00  26.05   29
 25  \w     38.00  84.00   1.00    3.00    --   70.00  73.00 152.64   46
 26  \w     38.00  65.00   1.00    3.00    --   70.00  73.00  56.60   27
 27  \w     39.00  69.00   1.00    3.00    --   70.00  74.00-134.73   30
 28  \w    100.00 144.00   1.00   12.00    --   74.00  55.00   6.17   44
 29  \w     51.00  78.00   1.00   12.00    --   74.00  55.00   6.17   27
 30  \w     46.00  73.00   1.00   12.00    --   74.00  57.00 -79.38   27
 31  \w     47.00  73.00   1.00   12.00    --   78.00  69.00  86.85   26
 32  \w     55.00  84.00   1.00   12.00    --   82.00  61.00 112.60   29
 33  \w     59.00  88.00   1.00   12.00    --   90.00  71.00 -60.05   29
 34  \w    110.00 168.00   1.00   12.00    --   94.00  74.00  25.66   58
 35  \w     62.00  96.00   1.00   12.00    --   94.00  74.00  25.66   34
 36  \w     77.00 149.00   1.00   12.00    --  105.15  61.00-150.00   72
 37  \w    123.00 150.00   1.00   12.00    --  105.15  61.00 150.00   27
 38  \w     76.00 103.00   1.00   12.00    --  105.15  61.00 150.00   27
 39  \w     79.00 126.00   1.00   12.00    --  105.15  61.00 -60.00   47
 40  \w     63.00 109.00   1.00   12.00    --  105.15-111.00  60.00   46
 41  \w     35.00 130.00   1.00   12.00    --  105.15 -45.00 -60.00   95
 42  \w     77.00 172.00   1.00   12.00    --  105.15  61.00   0.00   95
 43  \w    116.00 175.00   1.00   12.00    --  105.15  61.00-120.00   59
 44  \w     76.00 148.00   1.00   12.00    --  105.15  61.00 -30.00   72
 45  \w     76.00 104.00   1.00   12.00    --  105.15  61.00-120.00   28
 46  \w    110.00 174.00   1.00   12.00    --  105.15  61.00  60.00   64
 47  \w     76.00 103.00   1.00   12.00    --  105.15  61.00  60.00   27
 48  \w     28.00 107.00   1.00   12.00    --  105.15-108.00-151.00   79
 49  \w     77.00 158.00   1.00   12.00    --  105.15  61.00-180.00   81
 50  \w     66.00 125.00   1.00   12.00    --  105.15 178.00-120.00   59
 51  \w     76.00 162.00   1.00   12.00    --  105.15  61.00 120.00   86
 52  \w     33.00 106.00   1.00   12.00    --  105.15 -77.00 -90.00   73
 53  \w    112.00 171.00   1.00   12.00    --  105.15  61.00 -90.00   59
 54  \w     76.00 102.00   1.00   12.00    --  105.15  61.00 -90.00   26
 55  \w     30.00 105.00   1.00   12.00    --  105.15-111.00 120.00   75
 56  \w     81.00 108.00   1.00   12.00    --  105.15-111.00 -90.00   27
 57  \w     44.00  77.00   1.00   12.00    --  105.15-111.00 -90.00   33
 58  \w    115.00 174.00   1.00   12.00    --  105.15  61.00  90.00   59
 59  \w     76.00 103.00   1.00   12.00    --  105.15  61.00  90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            50406
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.662
_diffrn_reflns_theta_min         2.992
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.607
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.515
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       prism
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.231
_exptl_crystal_size_min          0.221
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 4585 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(7)
_refine_ls_extinction_coef       0.00098(13)
_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   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     808
_refine_ls_number_reflns         12132
_refine_ls_number_restraints     139
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0582P)^2^+0.2253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0961
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                11050
_reflns_number_total             12132
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12299_si_003.cif
_cod_data_source_block           qhn-1-943
_cod_original_cell_volume        3114.75(9)
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4134060
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.851
_shelx_estimated_absorpt_t_max   0.878
_shelx_res_checksum              5447
_shelx_hkl_checksum              40256