Identification of the Side Products That Diminish the Yields of the Monoamidated Product in Metal-Catalyzed C–H Amidation of 2-Phenylpyridine with Arylisocyanates
McKay, Alasdair I.; Altalhi, Weam A. O.; McInnes, Lachlan E.; Czyz, Milena L.; Canty, Allan J.; Donnelly, Paul S.; O’Hair, Richard A. J.; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.9b02831

data_4037832
_publ_section_title
;
 Identification of the Side Products That Diminish the Yields of the
 Monoamidated Product in Metal-Catalyzed C--H Amidation of
 2-Phenylpyridine with Arylisocyanates
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02831
_journal_year                    2020
_chemical_formula_moiety         'C18 H14 N2 O'
_chemical_formula_sum            'C18 H14 N2 O'
_chemical_formula_weight         274.31
_chemical_name_common            N-Phenyl-2-(pyridin-2-yl)benzamide
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.7276(19)
_cell_angle_beta                 90.133(2)
_cell_angle_gamma                102.615(3)
_cell_formula_units_Z            4
_cell_length_a                   8.3094(3)
_cell_length_b                   10.6542(3)
_cell_length_c                   16.6643(3)
_cell_measurement_reflns_used    8958
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.9090
_cell_measurement_theta_min      4.3650
_cell_volume                     1402.33(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.29a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.29a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.29a (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.965
_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     44.00  70.00   0.50    0.20    --   48.20  36.00  13.00   52
  2  \w     84.00 121.00   0.50    0.20    --   48.20  36.00  13.00   74
  3  \w     99.00 167.00   0.50    0.81    --  107.75  36.00  13.00  136
  4  \w    145.00 171.00   0.50    0.81    --  107.75 125.00 -30.00   52
  5  \w     96.00 172.00   0.50    0.81    --  107.75  45.00 -90.00  152
  6  \w     95.00 163.00   0.50    0.81    --  107.75  45.00  60.00  136
  7  \w     95.00 178.00   0.50    0.81    --  107.75  45.00  90.00  166
  8  \w    101.00 168.00   0.50    0.81    --  107.75  77.00 120.00  134
  9  \w     92.00 140.00   0.50    0.81    --  107.75 125.00 -30.00   96
 10  \w     35.00  69.00   0.50    0.81    --  107.75 -61.00  90.00   68
 11  \w     38.00 108.00   0.50    0.81    --  107.75 -94.00  90.00  140
 12  \w     89.00 117.00   0.50    0.81    --  107.75-125.00  90.00   56
 13  \w     81.00 109.00   0.50    0.81    --  107.75 -94.00  30.00   56
 14  \w     92.00 117.00   0.50    0.81    --  107.75-125.00   0.00   50
 15  \w     78.00 104.00   0.50    0.81    --  107.75 -94.00 -90.00   52
 16  \w     38.00 108.00   0.50    0.81    --  107.75 -94.00 -60.00  140
 17  \w     41.00  75.00   0.50    0.81    --  107.75 -94.00  30.00   68
 18  \w     36.00  86.00   0.50    0.81    --  107.75-125.00  90.00  100
 19  \w     36.00 101.00   0.50    0.81    --  107.75 -94.00   0.00  130
 20  \w     31.00  93.00   0.50    0.20    --   48.20-125.00-120.00  124
 21  \w     35.00  75.00   0.50    0.81    --  107.75 -94.00 -90.00   80
 22  \w     35.00 112.00   0.50    0.81    --  107.75-125.00-150.00  154
 23  \w     37.00 116.00   0.50    0.81    --  107.75-125.00 -90.00  158
 24  \w     35.00  86.00   0.50    0.81    --  107.75-125.00   0.00  102
 25  \w     43.00  68.00   0.50    0.81    --  107.75 -61.00 120.00   50
 26  \w    -26.00  10.00   0.50    0.20    --   48.20 -19.00  60.00   72
 27  \w    -26.00   5.00   0.50    0.20    --   48.20 -19.00 -90.00   62
 28  \w    -24.00  29.00   0.50    0.20    --   48.20 -36.00-143.00  106
 29  \w     35.00 117.00   0.50    0.81    --  107.75-125.00-120.00  164
 30  \w    -25.00  23.00   0.50    0.20    --  -48.20  36.00  13.00   96
 31  \w    -13.00  25.00   0.50    0.20    --  -48.20  77.00  60.00   76
 32  \w    -42.00 -17.00   0.50    0.81    --  -86.25  36.00  13.00   50
 33  \w    -71.00 -33.00   0.50    0.20    --  -48.20  77.00  60.00   76
 34  \w   -104.00 -79.00   0.50    0.81    --  -86.25 -36.00-143.00   50
 35  \w    -66.00 -39.00   0.50    0.20    --  -48.20 -36.00-143.00   54
 36  \w   -121.00 -70.00   0.50    0.20    --  -48.20 -36.00-143.00  102
 37  \w   -150.00-121.00   0.50    0.81    --  -86.25 -36.00-143.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0910130000
_diffrn_orient_matrix_UB_12      -0.1319872000
_diffrn_orient_matrix_UB_13      0.0185641000
_diffrn_orient_matrix_UB_21      -0.1612387000
_diffrn_orient_matrix_UB_22      0.0140493000
_diffrn_orient_matrix_UB_23      -0.0393108000
_diffrn_orient_matrix_UB_31      0.0437636000
_diffrn_orient_matrix_UB_32      -0.0743123000
_diffrn_orient_matrix_UB_33      -0.0843669000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16791
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.338
_diffrn_reflns_theta_min         4.366
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.650
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64615
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.29a (Rigaku Oxford Diffraction, 2018)
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    1.299
_exptl_crystal_description       prism
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     379
_refine_ls_number_reflns         5757
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0591P)^2^+0.5140P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1249
_refine_ls_wR_factor_ref         0.1303
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4964
_reflns_number_total             5757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02831_si_002.cif
_cod_data_source_block           3a
_cod_original_cell_volume        1402.32(7)
_cod_database_code               4037832
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     '2PhPy phenylamide'
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.926
_diffrn_oxdiff_digest_frames
;
01561cf3c62762736d842c759f900cd46b034921a98
;
_diffrn_oxdiff_digest_hkl
;
013ef5c9e80826980c72fbf88180b8c48464f3
;
_reflns_odcompleteness_completeness 98.35
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C14(H14), C25(H25), C7(H7), C28(H28), C18(H18), C9(H9),
 C15(H15), C26(H26), C36(H36), C8(H8), C22(H22), C4(H4A), C27(H27), C17(H17),
 C16(H16), C1(H1), C3(H3), C21(H21), C32(H32), C19(H19), C2(H2A), C20(H20),
 C33(H33), C10(H10), C35(H35), C34(H34)
;
_shelx_res_checksum              54789
_shelx_hkl_checksum              93058
_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 1.633
_oxdiff_exptl_absorpt_empirical_full_min 0.555