Asymmetric vicinal C(sp<sup>3</sup>)-H difunctionalization of saturated cyclic amines <i>via</i> synergistic photoredox, copper and chiral phosphoric acid catalysis.
Xiao, Teng-Fei; Jian, Ke-Rui; Gu, Yu-Cheng; Xu, Guo-Qiang; Xu, Peng-Fei; Chemical science 17 (2026) 3240–3247; doi:10.1039/d5sc06987d

data_1576508
_publ_section_title
;
 Asymmetric vicinal C(sp<sup>3</sup>)-H difunctionalization of saturated
 cyclic amines <i>via</i> synergistic photoredox, copper and chiral
 phosphoric acid catalysis.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              3240
_journal_page_last               3247
_journal_paper_doi               10.1039/d5sc06987d
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H26 N2 O2 S'
_chemical_formula_sum            'C27 H26 N2 O2 S'
_chemical_formula_weight         442.56
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-19
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-12-30 deposited with the CCDC.	2025-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.29790(10)
_cell_length_b                   11.78840(10)
_cell_length_c                   19.1733(2)
_cell_measurement_reflns_used    10514
_cell_measurement_temperature    275.80(10)
_cell_measurement_theta_max      77.0950
_cell_measurement_theta_min      4.2910
_cell_volume                     2327.56(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      275.80(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.972
_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     45.00  71.00   0.50    0.05    --  111.87-125.00-180.00   52
  2  \w     84.00 110.00   0.50    0.05    --  111.87-125.00-180.00   52
  3  \w    -56.00 -31.00   0.50    0.05    -- -100.00  61.00 120.00   50
  4  \w    -54.00 -27.00   0.50    0.05    -- -100.00  45.00   0.00   54
  5  \w    -53.00 -28.00   0.50    0.05    -- -100.00  45.00 -60.00   50
  6  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00 -90.00   50
  7  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00 120.00   50
  8  \w    -64.00 -39.00   0.50    0.05    -- -100.00  61.00 150.00   50
  9  \w   -128.00 -60.00   0.50    0.05    -- -100.00  83.00 166.00  136
 10  \w   -154.00 -94.00   0.50    0.05    -- -100.00 -94.00 -90.00  120
 11  \w   -109.00 -50.00   0.50    0.05    --  -44.30-179.00 -90.00  118
 12  \w     39.00  64.00   0.50    0.05    --  111.87 -61.00 -60.00   50
 13  \w     43.00  68.00   0.50    0.05    --  111.87 -61.00  30.00   50
 14  \w     40.00  68.00   0.50    0.05    --  111.87 -61.00 120.00   56
 15  \w     95.00 120.00   0.50    0.05    --  111.87  30.00  90.00   50
 16  \w     67.00 106.00   0.50    0.05    --   44.30  56.00 -55.00   78
 17  \w     25.00  64.00   0.50    0.05    --   44.30  56.00 -55.00   78
 18  \w     94.00 169.00   0.50    0.05    --  111.87  30.00-150.00  150
 19  \w    109.00 169.00   0.50    0.05    --  111.87  56.00 -55.00  120
 20  \w    134.00 160.00   0.50    0.05    --  111.87  30.00  90.00   52
 21  \w     96.00 172.00   0.50    0.05    --  111.87  85.00  58.00  152
 22  \w     24.00  61.00   0.50    0.05    --   44.30 -56.00 162.00   74
 23  \w    -27.00  17.00   0.50    0.05    --   44.30 -56.00 162.00   88
 24  \w    -29.00   4.00   0.50    0.05    --   44.30 -19.00-180.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0605207000
_diffrn_orient_matrix_UB_12      -0.1156703000
_diffrn_orient_matrix_UB_13      0.0185771000
_diffrn_orient_matrix_UB_21      0.0806519000
_diffrn_orient_matrix_UB_22      0.0034303000
_diffrn_orient_matrix_UB_23      -0.0676284000
_diffrn_orient_matrix_UB_31      0.1105385000
_diffrn_orient_matrix_UB_32      0.0606888000
_diffrn_orient_matrix_UB_33      0.0392057000
_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  0.0272
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13483
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.564
_diffrn_reflns_theta_min         4.403
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.438
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51217
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.179
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1719 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         4710
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0657P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0956
_refine_ls_wR_factor_ref         0.0977
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.924
_reflns_number_gt                4346
_reflns_number_total             4710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06987d2.cif
_cod_data_source_block           xiaotengfei-xpf_0719_auto
_cod_database_code               1576508
_shelx_shelxl_version_number     2018/3
_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 C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C14(H14), C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C9(H9), C11(H11), C12(H12), C15(H15),
 C16(H16), C18(H18), C19(H19), C27(H27)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C25(H25A,H25B,H25C)
2.e :
 C23(H23)
;
_shelx_res_checksum              64947
_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 1.567
_oxdiff_exptl_absorpt_empirical_full_min 0.648