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_4133827
_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         'C28 H30 B N O4, H2 O'
_chemical_formula_sum            'C28 H32 B N O5'
_chemical_formula_weight         473.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.6200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3572(2)
_cell_length_b                   10.32740(10)
_cell_length_c                   17.3961(2)
_cell_measurement_reflns_used    7074
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      70.8070
_cell_measurement_theta_min      4.0300
_cell_volume                     2578.33(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      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4670
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.975
_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   -112.00 -22.00   1.00    1.00    --  -42.25 -57.00  60.00   90
  2  \w   -112.00 -67.00   1.00    1.00    --  -42.25 -57.00 150.00   45
  3  \w    -92.00 -14.00   1.00    1.00    --  -42.25 125.00 -90.00   78
  4  \w     30.00  98.00   1.00    2.00    --  100.00 -61.00 -30.00   68
  5  \w     54.00 124.00   1.00    2.00    --  100.00 -30.00 -60.00   70
  6  \w     25.00  99.00   1.00    2.00    --  100.00 -94.00-150.00   74
  7  \w     78.00 171.00   1.00    2.00    --  100.00  45.00 120.00   93
  8  \w     32.00 119.00   1.00    2.00    --  100.00 -61.00  60.00   87
  9  \w     96.00 126.00   1.00    2.00    --  100.00 -61.00-150.00   30
 10  \w     30.00  56.00   1.00    2.00    --  100.00 -61.00-150.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1017101000
_diffrn_orient_matrix_UB_12      -0.0477547000
_diffrn_orient_matrix_UB_13      0.0008433000
_diffrn_orient_matrix_UB_21      -0.0064553000
_diffrn_orient_matrix_UB_22      -0.0185081000
_diffrn_orient_matrix_UB_23      -0.0878749000
_diffrn_orient_matrix_UB_31      0.0338048000
_diffrn_orient_matrix_UB_32      0.1400313000
_diffrn_orient_matrix_UB_33      -0.0113579000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0116
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10786
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.890
_diffrn_reflns_theta_min         4.049
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.663
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.285
_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    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             1008
_exptl_crystal_size_max          0.637
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.241
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     330
_refine_ls_number_reflns         4847
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0368
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0471P)^2^+0.6459P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0906
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4494
_reflns_number_total             4847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12297_si_005.cif
_cod_data_source_block           df13-17
_cod_database_code               4133827
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C28 H32 B N O5'
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.677
_reflns_odcompleteness_completeness 99.67
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26),
 C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34)
2.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              75349
_shelx_hkl_checksum              76942
_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 1.091
_oxdiff_exptl_absorpt_empirical_full_min 0.920