Photoinduced copper-catalysed enantioselective amination of allylic and propargylic C–H bonds
Dai, Ling; Chen, Ying-Ying; Wang, Jing-Jun; Chen, Jun-Jia; Zhou, Qi-Lin; Chemical Science 16 (2025) 9213–9219; doi:10.1039/D5SC00872G

data_1574416
_publ_section_title
;
 Photoinduced copper-catalysed enantioselective amination of allylic and
 propargylic C--H bonds
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9213
_journal_page_last               9219
_journal_paper_doi               10.1039/D5SC00872G
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H15 N O4'
_chemical_formula_sum            'C14 H15 N O4'
_chemical_formula_weight         261.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-20 deposited with the CCDC.	2025-04-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.1631(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.41048(5)
_cell_length_b                   6.29241(5)
_cell_length_c                   28.74880(18)
_cell_measurement_reflns_used    19269
_cell_measurement_temperature    143.15
_cell_measurement_theta_max      78.8460
_cell_measurement_theta_min      3.0740
_cell_volume                     1337.013(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      143.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -84.00  41.00   0.50    0.50    --  -48.80  35.00  55.00  250
  2  \w   -145.00 -21.00   0.50    0.50    -- -110.00  35.00  55.00  248
  3  \w   -199.00 -75.00   0.50    0.50    -- -110.00 -35.00-101.00  248
  4  \w    -84.00  35.00   0.50    0.50    --    5.00 -57.00-150.00  238
  5  \w   -138.00 -18.00   0.50    0.50    --  -48.80 -58.00 134.06  240
  6  \w   -138.00 -13.00   0.50    0.50    --  -48.80 -35.00-101.00  250
  7  \w    -79.00  41.00   0.50    0.50    --  -48.80  57.00-150.00  240
  8  \w   -138.00 -11.00   0.50    0.50    --  -48.80 -30.00 128.98  254
  9  \w   -140.00 -21.00   0.50    0.50    -- -110.00  57.00  60.00  238
 10  \w   -137.00 -39.00   0.50    0.50    -- -110.00  57.00 -90.00  196
 11  \w   -192.00-167.00   0.50    0.50    -- -110.00 -43.00  92.95   50
 12  \w   -128.00 -83.00   0.50    0.50    -- -110.00 -43.00  92.95   90
 13  \w   -111.00 -79.00   0.50    0.50    -- -110.00 -46.00-154.18   64
 14  \w   -198.00 -81.00   0.50    0.50    -- -110.00 -53.00  13.42  234
 15  \w   -198.00-150.00   0.50    0.50    -- -110.00 -62.00 160.07   96
 16  \w   -140.00 -22.00   0.50    0.50    -- -110.00  57.00-150.00  236
 17  \w   -102.00 -76.00   0.50    0.50    -- -110.00 -72.00 150.00   52
 18  \w   -102.00 -77.00   0.50    0.50    -- -110.00 -68.00-173.38   50
 19  \w   -101.00 -75.00   0.50    0.50    -- -110.00 -36.00 134.40   52
 20  \w   -164.00-138.00   0.50    0.50    -- -110.00 -59.00-162.59   52
 21  \w   -111.00 -80.00   0.50    0.50    -- -110.00 -59.00-162.59   62
 22  \w   -107.00 -81.00   0.50    0.50    -- -110.00 -61.00 148.94   52
 23  \w   -134.00-100.00   0.50    0.50    -- -110.00  38.00-150.00   68
 24  \w    -71.00 -21.00   0.50    0.50    -- -110.00  38.00-150.00  100
 25  \w   -185.00-159.00   0.50    0.50    -- -110.00 -46.00-154.18   52
 26  \w   -189.00-124.00   0.50    0.50    -- -110.00 -68.00-173.38  130
 27  \w   -145.00 -84.00   0.50    0.50    -- -110.00 -54.00-128.50  122
 28  \w    -50.00 -24.00   0.50    0.50    -- -110.00  57.00-120.00   52
 29  \w   -198.00-116.00   0.50    0.50    -- -110.00 -38.00   0.00  164
 30  \w   -108.00 -82.00   0.50    0.50    -- -110.00 -40.00 107.03   52
 31  \w   -106.00 -80.00   0.50    0.50    -- -110.00 -64.00 125.27   52
 32  \w   -140.00 -75.00   0.50    0.50    -- -110.00  57.00-120.00  130
 33  \w   -104.00 -79.00   0.50    0.50    -- -110.00 -62.00 160.07   50
 34  \w   -174.00 -75.00   0.50    0.50    -- -110.00 -36.00 145.84  198
 35  \w   -104.00 -77.00   0.50    0.50    -- -110.00 -38.00-180.00   54
 36  \w   -199.00-111.00   0.50    0.50    -- -110.00 -72.00 150.00  176
 37  \w   -175.00-146.00   0.50    0.50    -- -110.00 -42.00  99.12   58
 38  \w   -114.00 -78.00   0.50    0.50    -- -110.00 -42.00  99.12   72
 39  \w   -105.00 -79.00   0.50    0.50    -- -110.00 -70.00-159.18   52
 40  \w   -102.00 -75.00   0.50    0.50    -- -110.00 -36.00 119.22   54
 41  \w   -153.00-127.00   0.50    0.50    -- -110.00 -57.00-120.00   52
 42  \w   -109.00 -80.00   0.50    0.50    -- -110.00 -57.00-120.00   58
 43  \w   -105.00 -79.00   0.50    0.50    -- -110.00 -43.00 118.66   52
 44  \w   -104.00 -79.00   0.50    0.50    -- -110.00 -61.00 149.49   50
 45  \w   -119.00 -84.00   0.50    0.50    -- -110.00 -62.00  91.80   70
 46  \w   -103.00 -78.00   0.50    0.50    -- -110.00 -65.00 172.82   50
 47  \w   -109.00 -80.00   0.50    0.50    -- -110.00 -72.00 120.00   58
 48  \w   -114.00 -78.00   0.50    0.50    -- -110.00 -35.00 129.87   72
 49  \w   -106.00 -59.00   0.50    0.50    -- -110.00 -19.00 120.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0886055000
_diffrn_orient_matrix_UB_12      0.0998515000
_diffrn_orient_matrix_UB_13      0.0416374000
_diffrn_orient_matrix_UB_21      -0.1886225000
_diffrn_orient_matrix_UB_22      -0.0421986000
_diffrn_orient_matrix_UB_23      -0.0243832000
_diffrn_orient_matrix_UB_31      -0.0041496000
_diffrn_orient_matrix_UB_32      -0.2195596000
_diffrn_orient_matrix_UB_33      0.0236172000
_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  0.0246
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            24793
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.155
_diffrn_reflns_theta_min         3.082
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.795
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.01059
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       block
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 2337 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(5)
_refine_ls_extinction_coef       0.0032(5)
_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   1.109
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     358
_refine_ls_number_reflns         5663
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0592P)^2^+0.0773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0913
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.801
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                5490
_reflns_number_total             5663
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00872g2.cif
_cod_data_source_block           p20240809e
_cod_depositor_comments          'Adding full bibliography for 1574416.cif.'
_cod_original_cell_volume        1337.014(16)
_cod_database_code               1574416
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.832
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1 = N2-H2
 0.9 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C11(H11), C25(H25)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C18(H18), C19(H19), C21(H21), C22(H22)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              93706
_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 63.430
_oxdiff_exptl_absorpt_empirical_full_min 0.580