Photoinduced Metal-Free α-C(sp3)–H Carbamoylation of Saturated Aza-Heterocycles via Rationally Designed Organic Photocatalyst
Yi, Ming-Jun; Zhang, Huan-Xin; Xiao, Teng-Fei; Zhang, Ji-Hua; Feng, Zhi-Tao; Wei, Li-Pu; Xu, Guo-Qiang; Xu, Peng-Fei; ACS Catalysis 11 (2021) 3466–3472; doi:10.1021/acscatal.1c00242

data_4518533
_publ_section_title
;
 Photoinduced Metal-Free \a-C(sp3)--H Carbamoylation of Saturated
 Aza-Heterocycles via Rationally Designed Organic Photocatalyst
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3466
_journal_page_last               3472
_journal_paper_doi               10.1021/acscatal.1c00242
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C15 H22 N2 O'
_chemical_formula_sum            'C15 H22 N2 O'
_chemical_formula_weight         246.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-04-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.048(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7710(6)
_cell_length_b                   12.1463(5)
_cell_length_c                   9.6862(4)
_cell_measurement_reflns_used    1667
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.9680
_cell_measurement_theta_min      5.8320
_cell_volume                     1501.57(11)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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      1.00  28.00   1.00    1.00    --    0.00  57.00 -30.00   27
  2  \w     37.00  63.00   1.00    1.00    --    0.00  57.00 -30.00   26
  3  \w     53.00 115.00   1.00    1.00    --   54.00  57.00 -60.00   62
  4  \w    146.00 178.00   1.00    3.00    --  108.00  38.00 -30.00   32
  5  \w    102.00 130.00   1.00    3.00    --  108.00 -63.00-180.00   28
  6  \w     73.00 116.00   1.00    3.00    --  108.00-111.00-180.00   43
  7  \w     50.00  88.00   1.00    1.00    --   54.00-125.00-150.00   38
  8  \w    -16.00  16.00   1.00    1.00    --    0.00 -57.00-180.00   32
  9  \w    -13.00  84.00   1.00    1.00    --   54.00 -77.00-120.00   97
 10  \w     91.00 122.00   1.00    3.00    --  108.00  38.00 -30.00   31
 11  \w     45.00 129.00   1.00    3.00    --  108.00 -63.00  60.00   84
 12  \w     68.00 113.00   1.00    3.00    --  108.00-111.00  90.00   45
 13  \w     54.00 125.00   1.00    3.00    --  108.00 -63.00 150.00   71
 14  \w     86.00 137.00   1.00    3.00    --  108.00  50.00 150.00   51
 15  \w     35.00 130.00   1.00    3.00    --  108.00 -25.00 150.00   95
 16  \w     35.00 123.00   1.00    1.00    --   54.00  57.00-180.00   88
 17  \w    -68.00 -42.00   1.00    1.00    --    0.00 -57.00-180.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0365175000
_diffrn_orient_matrix_UB_12      0.0042657000
_diffrn_orient_matrix_UB_13      -0.1496221000
_diffrn_orient_matrix_UB_21      -0.1140616000
_diffrn_orient_matrix_UB_22      0.0183200000
_diffrn_orient_matrix_UB_23      -0.0523880000
_diffrn_orient_matrix_UB_31      0.0153238000
_diffrn_orient_matrix_UB_32      0.1254784000
_diffrn_orient_matrix_UB_33      0.0128886000
_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  0.0199
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            5224
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.550
_diffrn_reflns_theta_max         66.550
_diffrn_reflns_theta_min         5.845
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.536
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90055
_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            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.090
_exptl_crystal_description       block
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.117
_refine_diff_density_min         -0.109
_refine_diff_density_rms         0.025
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         2644
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0737P)^2^+0.0893P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1288
_refine_ls_wR_factor_ref         0.1428
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1926
_reflns_number_total             2644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00242_si_002.cif
_cod_data_source_block           zhanghx_0408
_cod_depositor_comments          'Adding full bibliography for 4518533.cif.'
_cod_database_code               4518533
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.61
_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)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C10(H10), C12(H12), C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              33533
_shelx_hkl_checksum              55979
_olex2_date_sample_data_collection 2020-04-08
_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 1.285
_oxdiff_exptl_absorpt_empirical_full_min 0.791