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_4133826
_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_absolute_configuration ad
_chemical_formula_moiety         'C25 H33 B N2 O4'
_chemical_formula_sum            'C25 H33 B N2 O4'
_chemical_formula_weight         436.34
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.0531(15)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.61682(10)
_cell_length_b                   16.7208(2)
_cell_length_c                   11.20335(16)
_cell_measurement_reflns_used    13091
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      70.8840
_cell_measurement_theta_min      4.1110
_cell_volume                     1185.02(3)
_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 1.000
_diffrn_measured_fraction_theta_max 0.995
_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 -37.00   1.00    1.00    --  -42.25 -38.00   0.00   75
  2  \w    -67.00  36.00   1.00    1.00    --  -42.25  19.00-180.00  103
  3  \w    -69.00  27.00   1.00    1.00    --  -42.25  57.00 -90.00   96
  4  \w     12.00  74.00   1.00    1.00    --   42.25 -99.00  30.00   62
  5  \w     57.00 110.00   1.00    2.00    --  100.00 -30.00 150.00   53
  6  \w     20.00 102.00   1.00    2.00    --  100.00 -94.00-150.00   82
  7  \w     85.00 130.00   1.00    2.00    --  100.00 -77.00-120.00   45
  8  \w     28.00 113.00   1.00    2.00    --  100.00-125.00  90.00   85
  9  \w     70.00 155.00   1.00    2.00    --  100.00  77.00 150.00   85
 10  \w     78.00 170.00   1.00    2.00    --  100.00  61.00  60.00   92
 11  \w     33.00  60.00   1.00    2.00    --  100.00 -61.00 -90.00   27
 12  \w     95.00 128.00   1.00    2.00    --  100.00 -61.00 -90.00   33
 13  \w    115.00 142.00   1.00    2.00    --  100.00 -15.00  60.00   27
 14  \w     64.00 118.00   1.00    2.00    --  100.00-125.00 -60.00   54
 15  \w     32.00  59.00   1.00    2.00    --  100.00 -15.00  60.00   27
 16  \w     21.00  47.00   1.00    2.00    --  100.00 -94.00-180.00   26
 17  \w     43.00 110.00   1.00    2.00    --  100.00 -94.00  90.00   67
 18  \w     58.00 166.00   1.00    2.00    --  100.00  15.00   0.00  108
 19  \w    -43.00  15.00   1.00    1.00    --  -42.25  96.00 -76.00   58
 20  \w      2.00  27.00   1.00    1.00    --   38.00  90.00  16.94   25
 21  \w    -70.00 -29.00   1.00    1.00    --  -42.25 -38.00 -90.00   41
 22  \w    -54.00 -16.00   1.00    1.00    --  -42.25 -57.00-180.00   38
 23  \w   -111.00 -62.00   1.00    1.00    --  -42.25 -57.00-180.00   49
 24  \w     17.00  43.00   1.00    1.00    --   42.25  57.00   0.00   26
 25  \w     18.00  44.00   1.00    1.00    --   50.00  82.00 132.32   26
 26  \w     18.00  43.00   1.00    1.00    --   50.00  80.00-153.58   25
 27  \w     18.00  45.00   1.00    1.00    --   50.00  80.00  95.65   27
 28  \w     18.00  43.00   1.00    1.00    --   50.00  81.00-110.75   25
 29  \w     18.00  43.00   1.00    1.00    --   50.00  81.00  54.76   25
 30  \w    102.00 127.00   1.00    1.00    --   54.00  75.00 -50.68   25
 31  \w     25.00  52.00   1.00    1.00    --   54.00  75.00 -50.68   27
 32  \w     31.00  60.00   1.00    1.00    --   62.00  77.00 124.11   29
 33  \w     91.00 118.00   1.00    1.00    --   62.00  76.00 179.57   27
 34  \w     32.00  57.00   1.00    1.00    --   62.00  74.00 -16.02   25
 35  \w     32.00  73.00   1.00    1.00    --   62.00  76.00 179.57   41
 36  \w     32.00  67.00   1.00    1.00    --   62.00  75.00  71.27   35
 37  \w     36.00  73.00   1.00    1.00    --   66.00  75.00 167.65   37
 38  \w     40.00  73.00   1.00    1.00    --   70.00  75.00   1.21   33
 39  \w     43.00  69.00   1.00    2.00    --   74.00  77.00-122.66   26
 40  \w     43.00  72.00   1.00    2.00    --   74.00  77.00 132.39   29
 41  \w     44.00  71.00   1.00    2.00    --   74.00  77.00 -90.49   27
 42  \w    104.00 135.00   1.00    2.00    --  100.00  77.00  30.00   31
 43  \w     69.00  98.00   1.00    2.00    --  100.00  77.00  30.00   29
 44  \w     69.00  95.00   1.00    2.00    --  100.00  77.00 -90.00   26
 45  \w     69.00  95.00   1.00    2.00    --  100.00  77.00 -30.00   26
 46  \w     73.00 100.00   1.00    2.00    --  100.00  61.00 -60.00   27
 47  \w     54.00 101.00   1.00    2.00    --  100.00 -61.00  90.00   47
 48  \w    134.00 171.00   1.00    2.00    --  100.00  77.00-120.00   37
 49  \w     98.00 131.00   1.00    2.00    --  100.00  77.00-120.00   33
 50  \w     69.00  96.00   1.00    2.00    --  100.00  77.00-120.00   27
 51  \w     69.00 135.00   1.00    2.00    --  100.00  77.00-180.00   66
 52  \w     99.00 171.00   1.00    2.00    --  100.00  77.00 120.00   72
 53  \w     71.00  98.00   1.00    2.00    --  100.00  77.00 120.00   27
 54  \w    124.00 166.00   1.00    2.00    --  100.00  77.00  90.00   42
 55  \w     69.00 123.00   1.00    2.00    --  100.00  77.00  90.00   54
 56  \w     74.00  99.00   1.00    2.00    --  100.00  61.00   0.00   25
 57  \w     72.00 117.00   1.00    2.00    --  100.00  77.00   0.00   45
 58  \w     69.00  97.00   1.00    2.00    --  100.00  77.00 -60.00   28
 59  \w     69.00  96.00   1.00    2.00    --  100.00  77.00  60.00   27
 60  \w     69.00 163.00   1.00    2.00    --  100.00  77.00-150.00   94
 61  \w    142.00 169.00   1.00    2.00    --  100.00  77.00 -90.00   27
;
_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      -0.1093107000
_diffrn_orient_matrix_UB_12      0.0572249000
_diffrn_orient_matrix_UB_13      -0.1072681000
_diffrn_orient_matrix_UB_21      -0.0119551000
_diffrn_orient_matrix_UB_22      0.0645544000
_diffrn_orient_matrix_UB_23      0.0957834000
_diffrn_orient_matrix_UB_31      0.2173048000
_diffrn_orient_matrix_UB_32      0.0323965000
_diffrn_orient_matrix_UB_33      -0.0013816000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0231
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            20860
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.887
_diffrn_reflns_theta_min         4.127
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.654
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.645
_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    1.223
_exptl_crystal_description       needle
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.701
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.144
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
The Flack x determined using 2019 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
is 0.05(6)
;
_refine_ls_abs_structure_Flack   -0.05(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         4509
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0465P)^2^+0.1427P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0768
_refine_ls_wR_factor_ref         0.0782
_reflns_Friedel_coverage         0.930
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                4357
_reflns_number_total             4509
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12297_si_004.cif
_cod_data_source_block           yl9-42-bpin
_cod_database_code               4133826
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C25 H33 B1 N2 O4'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.05(19)
 -0.05(19)
2. 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
3.a Ternary CH refined with riding coordinates:
 C13(H13)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C23(H23A,H23B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22)
3.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C)
;
_shelx_res_checksum              33548
_shelx_hkl_checksum              81563
_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 1.251
_oxdiff_exptl_absorpt_empirical_full_min 0.865