Harnessing the reactivity of captodative radicals: photocatalytic α-pyridination of glycyl derivatives through reversible radical coupling.
Yamazaki, Ken; Akimoto, Shuta; Miura, Tomoya; Organic & biomolecular chemistry 23 (2025) 9936–9941; doi:10.1039/d5ob00675a

data_7160590
_publ_section_title
;
 Harnessing the reactivity of captodative radicals: photocatalytic
 &#x3b1;-pyridination of glycyl derivatives through reversible radical
 coupling.
;
_journal_issue                   43
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9936
_journal_page_last               9941
_journal_paper_doi               10.1039/d5ob00675a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C16 H18 N2 O3'
_chemical_formula_sum            'C16 H18 N2 O3'
_chemical_formula_weight         286.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-07 deposited with the CCDC.	2025-06-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.978(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.4927(6)
_cell_length_b                   18.0971(12)
_cell_length_c                   11.2308(9)
_cell_measurement_reflns_used    3188
_cell_measurement_temperature    180.15
_cell_measurement_theta_max      29.1510
_cell_measurement_theta_min      3.5980
_cell_volume                     1477.8(2)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180.15
_diffrn_detector                 CCD
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.844
_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    -60.00 -33.00   0.50    1.01    --    5.00  18.00-120.00   54
  2  \w    -91.00  78.00   0.50    1.01    --  -11.30  55.00   0.00  338
  3  \w     27.00  74.00   0.50    1.01    --  -11.30  18.00  60.00   94
  4  \w    -77.00 -28.00   0.50    1.01    --  -11.30  18.00  60.00   98
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0863936000
_diffrn_orient_matrix_UB_12      -0.0172008000
_diffrn_orient_matrix_UB_13      0.0228829000
_diffrn_orient_matrix_UB_21      -0.0450355000
_diffrn_orient_matrix_UB_22      -0.0321424000
_diffrn_orient_matrix_UB_23      0.0141870000
_diffrn_orient_matrix_UB_31      -0.0033251000
_diffrn_orient_matrix_UB_32      -0.0144698000
_diffrn_orient_matrix_UB_33      -0.0592626000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.844
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            11009
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.768
_diffrn_reflns_theta_min         3.595
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.090
_exptl_crystal_colour            'clear yellowish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.68
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         3575
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0866
_refine_ls_R_factor_gt           0.0610
_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^)+(0.0928P)^2^+0.2791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1629
_refine_ls_wR_factor_ref         0.1765
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2442
_reflns_number_total             3575
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00675a2.cif
_cod_data_source_block           akimoto-product_autored
_cod_depositor_comments
'Adding full bibliography for 7160589--7160590.cif.'
_cod_database_code               7160590
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_usercomment     check1
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.941
_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:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 N7(H7), C18(H18), C6(H6), C5(H5), C17(H17), C20(H20), C2(H2), C3(H3), C21(H21)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              71990
_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 1.699
_oxdiff_exptl_absorpt_empirical_full_min 0.593