Cu-Catalyzed Intermolecular γ-Site C–H Amination of Cyclohexenone Derivatives: The Benefit of Bifunctional Ligands
Zhao, Xin; Yang, Fang; Zou, Shao-Yu; Zhou, Qian-Qian; Chen, Zi-Sheng; Ji, Kegong; ACS Catalysis  (2022) 1732–1741; doi:10.1021/acscatal.1c05439

data_4519306
_publ_section_title
;
 Cu-Catalyzed Intermolecular \g-Site C--H Amination of Cyclohexenone
 Derivatives: The Benefit of Bifunctional Ligands
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1732
_journal_page_last               1741
_journal_paper_doi               10.1021/acscatal.1c05439
_journal_year                    2022
_chemical_formula_moiety         'C36 H35 N3 O8'
_chemical_formula_sum            'C36 H35 N3 O8'
_chemical_formula_weight         637.67
_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             2020-06-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.05.22 svn.r1d9e7f8d for OlexSys, GUI svn.r6115)
;
_cell_angle_alpha                87.748(4)
_cell_angle_beta                 78.963(5)
_cell_angle_gamma                79.267(5)
_cell_formula_units_Z            2
_cell_length_a                   6.8134(5)
_cell_length_b                   14.9283(8)
_cell_length_c                   16.4870(9)
_cell_measurement_reflns_used    3745
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.0170
_cell_measurement_theta_min      2.7790
_cell_volume                     1617.11(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -13.00  82.00   1.00    4.00    --   11.74  37.00 120.00   95
  2  \w     11.00  38.00   1.00    4.00    --   11.74 -99.00   0.00   27
  3  \w    -13.00  52.00   1.00    4.00    --   11.74 -99.00 -30.00   65
  4  \w    -16.00  28.00   1.00    4.00    --  -11.59 -99.00-180.00   44
  5  \w     35.00  65.00   1.00    4.00    --   11.74 178.00 -30.00   30
  6  \w      7.00  86.00   1.00    4.00    --   11.74  37.00-150.00   79
  7  \w    -58.00 -32.00   1.00    4.00    --   11.74 -37.00 -60.00   26
;
_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      0.0516084000
_diffrn_orient_matrix_UB_12      -0.0433063000
_diffrn_orient_matrix_UB_13      -0.0158218000
_diffrn_orient_matrix_UB_21      0.0085811000
_diffrn_orient_matrix_UB_22      0.0178745000
_diffrn_orient_matrix_UB_23      -0.0407702000
_diffrn_orient_matrix_UB_31      0.0943347000
_diffrn_orient_matrix_UB_32      0.0119898000
_diffrn_orient_matrix_UB_33      0.0029641000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0799
_diffrn_reflns_av_unetI/netI     0.1004
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13346
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.517
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94154
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     429
_refine_ls_number_reflns         5679
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0994
_refine_ls_R_factor_gt           0.0703
_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^)+(0.0835P)^2^+0.0668P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3846
_reflns_number_total             5679
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05439_si_004.cif
_cod_data_source_block           exp_2160
_cod_original_cell_volume        1617.12(17)
_cod_database_code               4519306
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.987
_reflns_odcompleteness_completeness 99.94
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C24(H24),
 C25(H25), C27(H27), C28(H28), C32(H32), C33(H33), C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              9144
_shelx_hkl_checksum              16768
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.340
_oxdiff_exptl_absorpt_empirical_full_min 0.694