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_4519307
_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_absolute_configuration ad
_chemical_formula_moiety         'C23 H25 N5 O4'
_chemical_formula_sum            'C23 H25 N5 O4'
_chemical_formula_weight         435.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.09.11 svn.r3730fd0d for OlexSys, GUI svn.r6159)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.36481(13)
_cell_length_b                   17.9645(4)
_cell_length_c                   18.8399(4)
_cell_measurement_reflns_used    5809
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.5380
_cell_measurement_theta_min      3.3720
_cell_volume                     2154.17(8)
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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    -96.00  -2.00   1.00    1.00    --  -40.73 125.00-180.00   94
  2  \w   -113.00 -13.00   1.00    1.00    --  -40.73 -57.00-120.00  100
  3  \w     21.00 108.00   1.00    1.00    --   40.73  38.00-180.00   87
  4  \w     84.00 177.00   1.00    1.00    --  107.58  30.00 -60.00   93
  5  \w     26.00 103.00   1.00    1.00    --  107.58 -95.00  30.00   77
  6  \w    136.00 176.00   1.00    1.00    --  107.58 125.00  90.00   40
  7  \w     31.00 104.00   1.00    1.00    --  107.58 -30.00 120.00   73
  8  \w     43.00 137.00   1.00    1.00    --  107.58 -61.00-150.00   94
;
_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      -0.0272103000
_diffrn_orient_matrix_UB_12      -0.0165665000
_diffrn_orient_matrix_UB_13      0.0797145000
_diffrn_orient_matrix_UB_21      -0.0019659000
_diffrn_orient_matrix_UB_22      0.0841050000
_diffrn_orient_matrix_UB_23      0.0157924000
_diffrn_orient_matrix_UB_31      -0.2405422000
_diffrn_orient_matrix_UB_32      0.0012289000
_diffrn_orient_matrix_UB_33      -0.0091893000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            8253
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.725
_diffrn_reflns_theta_min         3.399
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.773
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71386
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(14)
_refine_ls_extinction_coef       0.0025(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4236
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.124
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0399P)^2^+0.6162P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.716
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                4057
_reflns_number_total             4236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05439_si_003.cif
_cod_data_source_block           yellow_0510
_cod_database_code               4519307
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C2(H2), C3(H3A), C4(H4), C5(H5), C6(H6), C12(H12), C19(H19), C21(H21),
  C22(H22)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              41703
_shelx_hkl_checksum              64647
_olex2_date_sample_data_collection 2021-05-10
_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 1.354
_oxdiff_exptl_absorpt_empirical_full_min 0.510