Palladium-Catalyzed C-N Bond Cleavage of 2 H-Azirines for the Synthesis of Functionalized α-Amido Ketones.
Xu, Fen; Si, Xiao-Ju; Song, Yuan-Yuan; Wang, Xing-Dong; Liu, Chun-Sen; Geng, Peng-Fei; Du, Miao; The Journal of organic chemistry 84 (2019) 2200–2208; doi:10.1021/acs.joc.8b03193

data_4033781
_publ_section_title
;
 Palladium-Catalyzed C-N Bond Cleavage of 2 H-Azirines for the Synthesis
 of Functionalized \a-Amido Ketones.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2200
_journal_page_last               2208
_journal_paper_doi               10.1021/acs.joc.8b03193
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C28 H40 N8 Pd'
_chemical_formula_sum            'C28 H40 N8 Pd'
_chemical_formula_weight         595.08
_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     iterative
_audit_creation_date             2018-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90.294(4)
_cell_angle_beta                 112.968(9)
_cell_angle_gamma                96.803(6)
_cell_formula_units_Z            1
_cell_length_a                   9.9466(10)
_cell_length_b                   11.2291(5)
_cell_length_c                   11.3124(6)
_cell_measurement_reflns_used    3177
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.3580
_cell_measurement_theta_min      4.2260
_cell_volume                     1153.32(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3031
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.958
_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    -61.00  32.00   1.00    4.49    --  -40.05  38.00 -60.00   93
  2  \w     47.00  80.00   1.00    4.49    --   40.05 -99.00 -90.00   33
  3  \w     66.00  96.00   1.00    4.49    --   40.05-125.00-150.00   30
  4  \w     42.00 113.00   1.00   17.95    --  108.39 -30.00 -60.00   71
  5  \w     91.00 138.00   1.00   17.95    --  108.39 -77.00 -90.00   47
  6  \w     69.00 108.00   1.00   17.95    --  108.39 -95.00 -90.00   39
  7  \w     39.00 132.00   1.00   17.95    --  108.39 -61.00-150.00   93
  8  \w     86.00 178.00   1.00   17.95    --  108.39  30.00 -60.00   92
  9  \w     94.00 177.00   1.00   17.95    --  108.39  30.00-120.00   83
 10  \w    151.00 178.00   1.00   17.95    --  108.39  45.00 120.00   27
 11  \w    151.00 178.00   1.00   17.95    --  108.39  45.00 150.00   27
 12  \w     84.00 111.00   1.00   17.95    --  108.39  45.00 150.00   27
 13  \w     32.00  98.00   1.00   17.95    --  108.39 -30.00 120.00   66
 14  \w     27.00  85.00   1.00   17.95    --  108.39 -95.00 120.00   58
 15  \w     42.00 120.00   1.00   17.95    --  108.39-125.00 120.00   78
 16  \w      5.00  47.00   1.00    4.49    --   40.05 -99.00-150.00   42
 17  \w     27.00 106.00   1.00   17.95    --  108.39 -95.00-180.00   79
 18  \w    -64.00  30.00   1.00    4.49    --  -40.05  57.00 150.00   94
 19  \w   -111.00 -16.00   1.00    4.49    --  -40.05 -57.00   0.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1594946000
_diffrn_orient_matrix_UB_12      0.0257472000
_diffrn_orient_matrix_UB_13      -0.0734988000
_diffrn_orient_matrix_UB_21      -0.0403936000
_diffrn_orient_matrix_UB_22      -0.0465092000
_diffrn_orient_matrix_UB_23      0.1113650000
_diffrn_orient_matrix_UB_31      0.0414811000
_diffrn_orient_matrix_UB_32      0.1277675000
_diffrn_orient_matrix_UB_33      0.0643598000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7583
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.380
_diffrn_reflns_theta_min         3.971
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.393
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    0.857
_exptl_crystal_F_000             310
_platon_squeeze_details
;
TITL sxj-jl-5_a.res in P-1
CELL    9.9466   11.2291   11.3124     90.29    112.97     96.80
SPGR P-1
C101 0.912 0.565 0.155 !       5.04 eA-3
C102 1.017 0.390 0.376 !       1.88 eA-3
C103 1.013 0.063 0.107 !       1.50 eA-3
C104 0.999 0.329 0.047 !       1.47 eA-3
C105 0.013 0.109 0.188 !       1.44 eA-3
C106 0.020 0.250 0.251 !       1.37 eA-3
C107 0.001 0.155 0.451 !       1.33 eA-3
C108 0.018 0.204 0.497 !       1.29 eA-3
Q109 0.495 0.517 0.077 !       1.27 eA-3
C110 0.022 0.171 0.219 !       1.24 eA-3
C111 1.008 1.001 0.048 !       1.12 eA-3
C112 0.980 0.781 0.408 !       1.12 eA-3
C113 1.009 0.814 0.207 !       1.09 eA-3
C114 0.042 0.126 0.314 !       1.09 eA-3
C115 1.018 0.952 0.141 !       1.06 eA-3
C116 0.994 0.796 0.252 !       1.05 eA-3
C117 1.015 0.862 0.111 !       1.03 eA-3
C118 0.038 0.096 0.393 !       1.01 eA-3
C119 0.009 0.282 0.171 !       1.01 eA-3
C120 0.008 0.890 0.219 !       0.97 eA-3
C121 1.012 0.890 0.405 !       0.80 eA-3
C122 0.995 0.672 0.472 !       0.77 eA-3
C123 0.960 0.690 0.252 !       0.74 eA-3
C124 0.970 0.717 0.205 !       0.73 eA-3
C125 0.010 0.019 0.465 !       0.71 eA-3
Q126 0.476 0.281 0.299 !       0.67 eA-3
C127 0.973 0.591 0.390 !       0.65 eA-3
C128 0.975 0.638 0.327 !       0.62 eA-3
Q129 0.592 0.497 0.031 !       0.58 eA-3
;
_refine_diff_density_max         1.134
_refine_diff_density_min         -0.645
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         4506
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0636
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0977P)^2^+0.0929P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1566
_refine_ls_wR_factor_ref         0.1671
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3861
_reflns_number_total             4506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b03193_si_005.cif
_cod_data_source_block           1
_cod_database_code               4033781
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C H O N Pd'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-C10 = N2-C11
 1.45 with sigma of 0.01
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C22(H22)
3.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C)
;
_platon_squeeze_void_probe_radius 1.20
_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 1.685
_oxdiff_exptl_absorpt_empirical_full_min 0.642