Precise construction of spiro stereocenters via enantioselective radical addition through modulating photocatalysis from redox to energy transfer
Liu, Fayu; Guo, Yanqi; Lu, Weidong; Zhao, Xiaowei; Yin, Yanli; Jiang, Zhiyong; Chemical Science 16 (2025) 10555–10562; doi:10.1039/D5SC01583A

data_1574597
_publ_section_title
;
 Precise construction of spiro stereocenters via enantioselective radical
 addition through modulating photocatalysis from redox to energy transfer
;
_journal_issue                   23
_journal_name_full               'Chemical Science'
_journal_page_first              10555
_journal_page_last               10562
_journal_paper_doi               10.1039/D5SC01583A
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H19 N3 S'
_chemical_formula_sum            'C18 H19 N3 S'
_chemical_formula_weight         309.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc2m16gc
_audit_creation_date             2024-07-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-01-03 deposited with the CCDC.	2025-05-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.820(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.1236(5)
_cell_length_b                   7.0187(3)
_cell_length_c                   12.0117(4)
_cell_measurement_reflns_used    5729
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.9160
_cell_measurement_theta_min      3.7170
_cell_volume                     1680.77(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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 1.000
_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    -52.00  35.00   1.00    1.00    --  -33.50  57.00-120.00   87
  2  \w   -102.00 -42.00   1.00    1.00    --  -33.50 -57.00-180.00   60
  3  \w   -102.00 -36.00   1.00    1.00    --  -33.50 -19.00 -30.00   66
  4  \w    -51.00  35.00   1.00    1.00    --  -33.50  57.00 -30.00   86
  5  \w    -34.00   4.00   1.00    1.00    --  -33.50 -19.00 -30.00   38
  6  \w     19.00  49.00   1.00    1.00    --   36.53  57.00 -60.00   30
  7  \w     69.00 100.00   1.00    1.00    --   36.53  37.00 -90.00   31
  8  \w     -1.00  24.00   1.00    1.00    --   36.53  95.00-136.54   25
  9  \w    -35.00  25.00   1.00    1.00    --   36.53 -19.00-150.00   60
 10  \w      2.00  27.00   1.00    1.00    --   36.53  91.00  47.61   25
 11  \w     65.00  93.00   1.00    1.00    --   36.53-130.00 100.00   28
 12  \w     21.00  68.00   1.00    1.00    --   36.53  57.00 150.00   47
 13  \w     27.00  58.00   1.00    1.00    --   36.53  57.00 120.00   31
 14  \w     19.00  63.00   1.00    1.00    --   36.53  57.00  90.00   44
 15  \w    -25.00  25.00   1.00    1.00    --   36.53 -57.00  90.00   50
 16  \w    -14.00  50.00   1.00    1.00    --   36.53 -57.00  30.00   64
 17  \w     46.00  92.00   1.00    1.00    --   36.53-139.00 -73.00   46
 18  \w     72.00 106.00   1.00    1.00    --   36.53  19.00-120.00   34
 19  \w     -1.00  24.00   1.00    1.00    --   36.53  95.00 169.74   25
 20  \w     28.00  94.00   1.00    1.00    --   36.53  57.00 -30.00   66
 21  \w    -25.00   2.00   1.00    1.00    --   36.53 -57.00   0.00   27
 22  \w     39.00  73.00   1.00    1.00    --   36.53 -19.00-150.00   34
 23  \w     -1.00  27.00   1.00    1.00    --   36.53  93.00 107.51   28
 24  \w     11.00  60.00   1.00    1.00    --   36.53 -77.00   0.00   49
 25  \w     30.00  55.00   1.00    1.00    --   36.53 -57.00   0.00   25
 26  \w    -16.00  65.00   1.00    1.00    --   36.53 -77.00 150.00   81
 27  \w     69.00  96.00   1.00    1.00    --   36.53  57.00 120.00   27
 28  \w     23.00  71.00   1.00    1.00    --   36.53  19.00-120.00   48
 29  \w     10.00  37.00   1.00    1.00    --   36.53  73.00  10.25   27
 30  \w     44.00  71.00   1.00    1.00    --   36.53  73.00  10.25   27
 31  \w     13.00  63.00   1.00    1.00    --   36.53  67.00-139.47   50
 32  \w    127.00 175.00   1.00    4.00    --  108.00  61.00-120.00   48
 33  \w     85.00 112.00   1.00    4.00    --  108.00  30.00  60.00   27
 34  \w     88.00 114.00   1.00    4.00    --  108.00  61.00-120.00   26
 35  \w     49.00 109.00   1.00    4.00    --  108.00-111.00 -60.00   60
 36  \w    119.00 176.00   1.00    4.00    --  108.00  45.00-150.00   57
 37  \w    135.00 170.00   1.00    4.00    --  108.00  61.00 -60.00   35
 38  \w     40.00  81.00   1.00    4.00    --  108.00 -77.00 120.00   41
 39  \w     89.00 119.00   1.00    4.00    --  108.00  61.00 -60.00   30
 40  \w     83.00 113.00   1.00    4.00    --  108.00  30.00-180.00   30
 41  \w     84.00 109.00   1.00    4.00    --  108.00-111.00 120.00   25
 42  \w    130.00 163.00   1.00    4.00    --  108.00  61.00 120.00   33
 43  \w    124.00 167.00   1.00    4.00    --  108.00  61.00   0.00   43
 44  \w     90.00 119.00   1.00    4.00    --  108.00  61.00 120.00   29
 45  \w     41.00  78.00   1.00    4.00    --  108.00-111.00 120.00   37
 46  \w     83.00 111.00   1.00    4.00    --  108.00  30.00 120.00   28
 47  \w     89.00 114.00   1.00    4.00    --  108.00  61.00   0.00   25
 48  \w     90.00 123.00   1.00    4.00    --  108.00  61.00  90.00   33
 49  \w    134.00 171.00   1.00    4.00    --  108.00  61.00  90.00   37
 50  \w     89.00 114.00   1.00    4.00    --  108.00  45.00 -60.00   25
 51  \w     68.00  95.00   1.00    4.00    --  108.00-111.00  90.00   27
 52  \w    134.00 175.00   1.00    4.00    --  108.00  61.00 -90.00   41
 53  \w    124.00 176.00   1.00    4.00    --  108.00  61.00 -30.00   52
 54  \w     88.00 118.00   1.00    4.00    --  108.00  45.00-150.00   30
 55  \w    129.00 171.00   1.00    4.00    --  108.00  61.00  60.00   42
 56  \w     39.00 100.00   1.00    4.00    --  108.00 -94.00-180.00   61
 57  \w     89.00 117.00   1.00    4.00    --  108.00  61.00 -90.00   28
 58  \w     88.00 115.00   1.00    4.00    --  108.00  45.00 -30.00   27
 59  \w     89.00 114.00   1.00    4.00    --  108.00  61.00 -30.00   25
 60  \w     89.00 116.00   1.00    4.00    --  108.00  45.00 -90.00   27
 61  \w     88.00 115.00   1.00    4.00    --  108.00  61.00  60.00   27
 62  \w     82.00 109.00   1.00    4.00    --  108.00  30.00 -90.00   27
 63  \w    136.00 176.00   1.00    4.00    --  108.00  61.00  30.00   40
 64  \w     89.00 114.00   1.00    4.00    --  108.00  61.00  30.00   25
 65  \w     46.00 127.00   1.00    4.00    --  108.00 -61.00 -60.00   81
 66  \w     85.00 114.00   1.00    4.00    --  108.00  30.00 150.00   29
 67  \w     83.00 108.00   1.00    4.00    --  108.00  30.00  30.00   25
 68  \w     83.00 108.00   1.00    4.00    --  108.00  30.00  90.00   25
 69  \w     89.00 114.00   1.00    4.00    --  108.00  45.00  30.00   25
 70  \w     85.00 113.00   1.00    4.00    --  108.00  30.00 -30.00   28
 71  \w     88.00 114.00   1.00    4.00    --  108.00  45.00  90.00   26
 72  \w     89.00 114.00   1.00    4.00    --  108.00  45.00  60.00   25
 73  \w     89.00 118.00   1.00    4.00    --  108.00  61.00-180.00   29
 74  \w    122.00 173.00   1.00    4.00    --  108.00  61.00 150.00   51
 75  \w     85.00 116.00   1.00    4.00    --  108.00  30.00   0.00   31
 76  \w     39.00  68.00   1.00    4.00    --  108.00 -94.00 -30.00   29
 77  \w     78.00 103.00   1.00    4.00    --  108.00 -94.00 -30.00   25
 78  \w    153.00 178.00   1.00    4.00    --  108.00  45.00-180.00   25
 79  \w     89.00 114.00   1.00    4.00    --  108.00  45.00 120.00   25
 80  \w     88.00 116.00   1.00    4.00    --  108.00  45.00-180.00   28
 81  \w     89.00 114.00   1.00    4.00    --  108.00  61.00 150.00   25
 82  \w    103.00 136.00   1.00    4.00    --  108.00 -77.00 120.00   33
 83  \w     85.00 118.00   1.00    4.00    --  108.00  36.00-115.67   33
;
_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      0.0451428000
_diffrn_orient_matrix_UB_12      -0.0104509000
_diffrn_orient_matrix_UB_13      -0.0936869000
_diffrn_orient_matrix_UB_21      0.0621449000
_diffrn_orient_matrix_UB_22      -0.0218331000
_diffrn_orient_matrix_UB_23      0.0892607000
_diffrn_orient_matrix_UB_31      -0.0083678500
_diffrn_orient_matrix_UB_32      -0.2181317500
_diffrn_orient_matrix_UB_33      -0.0043789000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11325
_diffrn_reflns_point_group_measured_fraction_full 0.877
_diffrn_reflns_point_group_measured_fraction_max 0.866
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.853
_diffrn_reflns_theta_min         3.714
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.694
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.223
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 867 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2804
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0673P)^2^+0.3280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1186
_reflns_Friedel_coverage         0.599
_reflns_Friedel_fraction_full    0.731
_reflns_Friedel_fraction_max     0.711
_reflns_number_gt                2512
_reflns_number_total             2804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01583a2.cif
_cod_data_source_block           202407jzy1_auto
_cod_depositor_comments          'Adding full bibliography for 1574597.cif.'
_cod_original_cell_volume        1680.77(9)
_cod_database_code               1574597
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H2N2O4S1
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.717
_reflns_odcompleteness_completeness 100.00
_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 C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C9(H9A,H9B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C13(H13), C14(H14), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              27964
_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 1.222
_oxdiff_exptl_absorpt_empirical_full_min 0.812