Direct Access to Chiral Secondary Amides by Copper-Catalyzed Borylative Carboxamidation of Vinylarenes with Isocyanates.
Fiorito, Daniele; Liu, Yangbin; Besnard, Celine; Mazet, Clément; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b12297

data_4133828
_publ_section_title
;
 Direct Access to Chiral Secondary Amides by Copper-Catalyzed Borylative
 Carboxamidation of Vinylarenes with Isocyanates.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b12297
_journal_year                    2019
_chemical_formula_moiety         'C20 H28 B N O3'
_chemical_formula_sum            'C20 H28 B N O3'
_chemical_formula_weight         341.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3190(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9466(3)
_cell_length_b                   8.57729(14)
_cell_length_c                   11.94065(18)
_cell_measurement_reflns_used    3106
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.9990
_cell_measurement_theta_min      5.7040
_cell_volume                     1830.15(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_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 0.998
_diffrn_measured_fraction_theta_max 0.977
_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    -65.00  33.00   1.00   10.00    --  -40.91  38.00 -60.00   98
  2  \w    -68.00  30.00   1.00   10.00    --  -40.91  57.00-180.00   98
  3  \w     30.00  75.00   1.00   10.00    --   40.91-125.00  60.00   45
  4  \w     27.00 109.00   1.00   40.00    --  107.03 -94.00 -30.00   82
  5  \w     49.00  84.00   1.00   40.00    --  107.03 -94.00-120.00   35
  6  \w     39.00 106.00   1.00   40.00    --  107.03-125.00-120.00   67
  7  \w    103.00 170.00   1.00   40.00    --  107.03  45.00 -30.00   67
  8  \w    149.00 176.00   1.00   40.00    --  107.03 125.00-180.00   27
  9  \w     94.00 166.00   1.00   40.00    --  107.03 125.00-120.00   72
 10  \w     78.00 172.00   1.00   40.00    --  107.03  61.00  60.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0256155000
_diffrn_orient_matrix_UB_12      0.1644777000
_diffrn_orient_matrix_UB_13      -0.0315444000
_diffrn_orient_matrix_UB_21      -0.0105694000
_diffrn_orient_matrix_UB_22      0.0572724000
_diffrn_orient_matrix_UB_23      0.1197956000
_diffrn_orient_matrix_UB_31      0.0815830000
_diffrn_orient_matrix_UB_32      -0.0442039000
_diffrn_orient_matrix_UB_33      0.0380623000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7081
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.574
_diffrn_reflns_theta_min         4.950
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.671
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.238
_exptl_crystal_description       needle
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.488
_exptl_crystal_size_mid          0.024
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.0007(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     234
_refine_ls_number_reflns         3604
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0525P)^2^+0.4783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1014
_refine_ls_wR_factor_ref         0.1083
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3009
_reflns_number_total             3604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12297_si_003.cif
_cod_data_source_block           df12-41
_cod_database_code               4133828
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C20 H28 B1 N1 O3'
_reflns_odcompleteness_completeness 99.89
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C12(H12), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C)
;
_shelx_res_checksum              24313
_shelx_hkl_checksum              3847
_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 1.528
_oxdiff_exptl_absorpt_empirical_full_min 0.737