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_4519305
_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         'C19 H17 N O'
_chemical_formula_sum            'C19 H17 N O'
_chemical_formula_weight         275.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.2423(10)
_cell_length_b                   15.2953(4)
_cell_length_c                   7.4169(2)
_cell_measurement_reflns_used    2775
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.4460
_cell_measurement_theta_min      3.3050
_cell_volume                     2977.02(16)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      100.01(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 0.977
_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    -27.00   0.00   1.00    1.00    --   40.98 -38.00 -30.00   27
  2  \w     36.00  66.00   1.00    1.00    --   40.98 -38.00 -30.00   30
  3  \w     36.00  63.00   1.00    1.00    --   40.98 -99.00-150.00   27
  4  \w     24.00 103.00   1.00    1.50    --  106.95 -94.00-180.00   79
  5  \w     54.00 174.00   1.00    1.50    --  106.95   0.00-120.00  120
  6  \w    133.00 177.00   1.00    1.50    --  106.95 106.00-146.00   44
  7  \w    142.00 175.00   1.00    1.50    --  106.95 125.00-180.00   33
  8  \w   -111.00 -16.00   1.00    1.00    --  -40.98 -38.00-180.00   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      0.0147353000
_diffrn_orient_matrix_UB_12      -0.0937464000
_diffrn_orient_matrix_UB_13      -0.0551204000
_diffrn_orient_matrix_UB_21      0.0565991000
_diffrn_orient_matrix_UB_22      0.0267336000
_diffrn_orient_matrix_UB_23      -0.0035107000
_diffrn_orient_matrix_UB_31      0.0050381000
_diffrn_orient_matrix_UB_32      -0.0253539000
_diffrn_orient_matrix_UB_33      0.2002359000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            7296
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.563
_diffrn_reflns_theta_min         3.344
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65109
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         2930
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0639
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0639P)^2^+1.4234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1354
_refine_ls_wR_factor_ref         0.1431
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2489
_reflns_number_total             2930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05439_si_002.cif
_cod_data_source_block           exp_1822
_cod_database_code               4519305
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.927
_reflns_odcompleteness_completeness 99.93
_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
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O1-C17 \\sim O2-C17
 with sigma of 0.02
3. Rigid bond restraints
 O2, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O2 \\sim C17: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
Uanis(O2) \\sim Ueq: with sigma of 0.00002 and sigma for terminal atoms of
0.00004
5. Others
 Sof(O2)=Sof(H2A)=1-FVAR(1)
 Sof(O1)=Sof(H1)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C4(H4), C3(H3), C2(H2), C15(H15), C16(H16), C18(H18),
 C19(H19), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
6.c Tetrahedral OH refined with riding coordinates:
 O1(H1), O2(H2A)
;
_shelx_res_checksum              33501
_shelx_hkl_checksum              10554
_olex2_date_sample_data_collection 2019-05-17
_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 1.410
_oxdiff_exptl_absorpt_empirical_full_min 0.658