Metal-free amination of alkenes based on maleimides.
Shen, Li-Wen; Lei, Shuang-Ling; Wang, Hong-Yan; Wang, Xin; Lu, Lin-Mu; Wang, Guang-Wei; Jia, Yun-Qing; Xiang, Min; Organic & biomolecular chemistry 23 (2025) 3865–3869; doi:10.1039/d5ob00201j

data_7160422
_publ_section_title
;
 Metal-free amination of alkenes based on maleimides.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3865
_journal_page_last               3869
_journal_paper_doi               10.1039/d5ob00201j
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C18 H14 N2 O4'
_chemical_formula_sum            'C18 H14 N2 O4'
_chemical_formula_weight         322.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2021-12-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-06-05 deposited with the CCDC.	2025-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.3771(2)
_cell_length_b                   7.62053(17)
_cell_length_c                   33.9209(7)
_cell_measurement_reflns_used    2997
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.0120
_cell_measurement_theta_min      6.3170
_cell_volume                     3199.42(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_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    -64.00 -38.80   0.60    1.00    --    0.00 147.00 164.00   42
  2  \w    -50.00 -24.80   0.60    1.00    --    0.00 124.00   0.00   42
  3  \w    -79.00 -53.80   0.60    1.75    --  -33.50 147.00 164.00   42
  4  \w     51.00  80.40   0.60    1.75    --   36.47-124.00 -79.00   49
  5  \w     44.00 101.60   0.60    1.75    --   36.47-147.00 115.00   96
  6  \w    117.00 143.40   0.60    7.50    --  108.00 124.00   0.00   44
  7  \w    102.00 159.00   0.60    7.50    --  108.00 147.00 164.00   95
  8  \w     62.00  87.20   0.60    7.50    --  108.00-147.00 115.00   42
  9  \w     56.00  82.40   0.60    7.50    --  108.00-124.00 -79.00   44
 10  \w    -77.00  -6.80   0.60    1.75    --  -33.50 -77.00 -60.00  117
 11  \w    -18.00   9.00   0.60    1.75    --   36.47 -57.00 120.00   45
 12  \w     60.00  93.00   0.60    1.75    --   36.47 178.00   0.00   55
 13  \w     23.00  53.00   0.60    1.75    --   36.47 -57.00 120.00   50
 14  \w     18.00 103.20   0.60    1.75    --   36.47  57.00 -60.00  142
 15  \w     62.00 107.60   0.60    1.75    --   36.47 178.00-120.00   76
 16  \w     61.00  97.60   0.60    1.75    --   36.47 178.00  30.00   61
 17  \w     69.00 150.00   0.60    7.50    --  108.00 178.00-120.00  135
 18  \w     69.00 126.60   0.60    7.50    --  108.00 -61.00  90.00   96
 19  \w     87.00 118.20   0.60    7.50    --  108.00 -61.00-120.00   52
 20  \w    100.00 177.40   0.60    7.50    --  108.00 111.00-150.00  129
 21  \w     88.00 174.40   0.60    7.50    --  108.00  45.00 -90.00  144
 22  \w     59.60 110.00   0.60    7.50    --  108.00 -94.00-180.00   84
 23  \w    114.00 140.40   0.60    7.50    --  108.00  61.00  90.00   44
 24  \w     88.00 113.20   0.60    7.50    --  108.00  61.00  90.00   42
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0638546000
_diffrn_orient_matrix_UB_12      0.0781116000
_diffrn_orient_matrix_UB_13      -0.0348087000
_diffrn_orient_matrix_UB_21      -0.0862927000
_diffrn_orient_matrix_UB_22      0.0687902000
_diffrn_orient_matrix_UB_23      0.0288376000
_diffrn_orient_matrix_UB_31      0.0630100000
_diffrn_orient_matrix_UB_32      0.1733624000
_diffrn_orient_matrix_UB_33      0.0042644000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            12816
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.033
_diffrn_reflns_theta_max         67.033
_diffrn_reflns_theta_min         4.422
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.797
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.034
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     216
_refine_ls_number_reflns         2847
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0487
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0743P)^2^+0.4685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1320
_refine_ls_wR_factor_ref         0.1465
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2238
_reflns_number_total             2847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00201j2.cif
_cod_data_source_block           202112368
_cod_depositor_comments          'Adding full bibliography for 7160422.cif.'
_cod_database_code               7160422
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N2
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.897
_reflns_odcompleteness_completeness 99.91
_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,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C16A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C17) = Uanis(C17A)
Uanis(C18) = Uanis(C18A)
3. Others
 Sof(H12C)=Sof(H12D)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C13A)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C18)=Sof(H18)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=
 Sof(C15)=Sof(H15)=Sof(C14)=Sof(H14)=Sof(C13)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C12(H12C,H12D)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C14A(H14A), C15A(H15A),
 C16A(H16A), C17A(H17A), C18A(H18A), C18(H18), C17(H17), C16(H16), C15(H15),
 C14(H14)
4.c Fitted hexagon refined as free rotating group:
 C14A(C15A,C16A,C17A,C18A,C13A), C18(C17,C16,C15,C14,C13)
;
_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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.843