Ruthenium-catalyzed ortho-selective CAr-H amination of heteroaryl arenes with di-tert-butyldiaziridinone
Gou, Xue-Ya; Li, Yuke; Wang, Xin-Gang; Liu, Hong-Chao; Zhang, Bo-Sheng; Zhao, Jiahui; Zhou, Zhao-Zhao; Liang, Yong-Min; Chemical Communications  (2019) –; doi:10.1039/C9CC02499A

data_7123298
_publ_section_title
;
 Ruthenium-catalyzed ortho-selective CAr-H amination of heteroaryl arenes
 with di-tert-butyldiaziridinone
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC02499A
_journal_year                    2019
_chemical_formula_moiety         'C15 H17 Br N2'
_chemical_formula_sum            'C15 H17 Br N2'
_chemical_formula_weight         305.21
_chemical_name_systematic        5-bromo-N-(tert-butyl)-2-(pyridin-2-yl)aniline
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_symmetry_space_group_name_Hall  'F 2 -2d'
_symmetry_space_group_name_H-M   'F d d 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-21 deposited with the CCDC.    2019-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   36.666(4)
_cell_length_b                   16.9718(19)
_cell_length_c                   9.1422(8)
_cell_measurement_reflns_used    914
_cell_measurement_temperature    294.37(10)
_cell_measurement_theta_max      21.8930
_cell_measurement_theta_min      4.2720
_cell_volume                     5689.1(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.37(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -61.00  -36.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4273  -57.0000  -60.0000 25

  2 omega  -45.00   75.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -19.0000   60.0000 120
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0021232000
_diffrn_orient_matrix_UB_12      0.0393043000
_diffrn_orient_matrix_UB_13      -0.0249729000
_diffrn_orient_matrix_UB_21      0.0146857000
_diffrn_orient_matrix_UB_22      0.0053967000
_diffrn_orient_matrix_UB_23      0.0494720000
_diffrn_orient_matrix_UB_31      0.0124087000
_diffrn_orient_matrix_UB_32      -0.0131540000
_diffrn_orient_matrix_UB_33      -0.0542998000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.710
_diffrn_reflns_av_R_equivalents  0.0509
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            3346
_diffrn_reflns_point_group_measured_fraction_full 0.718
_diffrn_reflns_point_group_measured_fraction_max 0.706
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         25.971
_diffrn_reflns_theta_min         3.755
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.875
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56895
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             2496
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: petroleum ether/ethyl acetate'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.023(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         1977
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0695P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1221
_refine_ls_wR_factor_ref         0.1349
_reflns_Friedel_coverage         0.329
_reflns_Friedel_fraction_full    0.398
_reflns_Friedel_fraction_max     0.374
_reflns_number_gt                1504
_reflns_number_total             1977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc02499a2.cif
_cod_data_source_block           gouxy_1106
_cod_database_code               7123298
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.724
_shelx_estimated_absorpt_t_min   0.626
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2.a Aromatic/amide H refined with riding coordinates:
 N2(H2), C8(H8), C11(H11), C4(H4), C10(H10), C2(H2A), C1(H1), C3(H3)
2.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              37336
_olex2_date_sample_data_collection 2018-11-07
_olex2_submission_special_instructions 'No special instructions were received'