PIDA-mediated synthesis of kynurenine derivatives by oxidative fragmentation of the tryptophan scaffold.
Jena, Chinmay K.; Patnaik, Aurobindo; Nayak, Sushree S.; Kumari, Supriya; Panda, Ankita; Dixit, Manjusha; Sharma, Nagendra K.; Organic & biomolecular chemistry 23 (2025) 3208–3223; doi:10.1039/d5ob00057b

data_7160390
_publ_section_title
;
 PIDA-mediated synthesis of kynurenine derivatives by oxidative
 fragmentation of the tryptophan scaffold.
;
_journal_issue                   13
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3208
_journal_page_last               3223
_journal_paper_doi               10.1039/d5ob00057b
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration s
_chemical_formula_moiety         '2(C19 H20 N2 O6 S)'
_chemical_formula_sum            'C38 H40 N4 O12 S2'
_chemical_formula_weight         808.86
_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             2024-04-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-09-30 deposited with the CCDC.	2025-02-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.994(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0125(2)
_cell_length_b                   8.54110(10)
_cell_length_c                   21.0020(3)
_cell_measurement_reflns_used    12718
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.0770
_cell_measurement_theta_min      4.1240
_cell_volume                     1908.17(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_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  31.00   0.50    0.55    --  -38.50  18.00 149.00  152
  2  \w   -108.00 -32.00   0.50    0.55    --  -38.50 -18.00 -18.00  152
  3  \w     43.00 118.00   0.50    0.55    --   48.81  18.00 149.00  150
  4  \w    -21.00  55.00   0.50    0.55    --   48.81 -18.00 -18.00  152
  5  \w     33.00 108.00   0.50    2.77    --  102.00 -18.00 -18.00  150
  6  \w     96.00 172.00   0.50    2.77    --  102.00  18.00 149.00  152
  7  \w    -50.00  24.00   0.50    0.55    --  -38.50  57.00 -30.00  148
  8  \w    -42.00  28.00   0.50    0.55    --  -38.50  38.00 -90.00  140
  9  \w     46.00 115.00   0.50    0.55    --   48.81  38.00-180.00  138
 10  \w     38.00 107.00   0.50    2.77    --  102.00 -45.00-150.00  138
 11  \w     34.00 105.00   0.50    2.77    --  102.00 -30.00 -60.00  142
 12  \w     39.00 105.00   0.50    2.77    --  102.00 -61.00-120.00  132
 13  \w     39.00  65.00   0.50    2.77    --  102.00-125.00   0.00   52
 14  \w    131.00 164.00   0.50    2.77    --  102.00 125.00 -60.00   66
 15  \w     79.00 105.00   0.50    2.77    --  102.00-125.00   0.00   52
 16  \w     40.00  74.00   0.50    2.77    --  102.00-125.00-120.00   68
 17  \w     77.00 107.00   0.50    2.77    --  102.00-125.00-120.00   60
 18  \w     43.00 111.00   0.50    2.77    --  102.00-125.00  30.00  136
 19  \w    100.00 161.00   0.50    2.77    --  102.00  30.00  90.00  122
 20  \w    109.00 144.00   0.50    2.77    --  102.00  77.00  30.00   70
 21  \w     98.00 126.00   0.50    2.77    --  102.00 125.00 -60.00   56
 22  \w     78.00 104.00   0.50    2.77    --  102.00 -94.00-150.00   52
 23  \w     40.00 106.00   0.50    2.77    --  102.00-125.00-150.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1346569000
_diffrn_orient_matrix_UB_12      -0.0170498000
_diffrn_orient_matrix_UB_13      0.0078473000
_diffrn_orient_matrix_UB_21      -0.0012284000
_diffrn_orient_matrix_UB_22      0.1753336000
_diffrn_orient_matrix_UB_23      0.0170149000
_diffrn_orient_matrix_UB_31      -0.0533461000
_diffrn_orient_matrix_UB_32      0.0387931000
_diffrn_orient_matrix_UB_33      -0.0735792000
_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  0.0544
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            16144
_diffrn_reflns_point_group_measured_fraction_full 0.902
_diffrn_reflns_point_group_measured_fraction_max 0.856
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.421
_diffrn_reflns_theta_min         4.156
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.858
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82084
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.002
_refine_diff_density_max         0.285
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2437 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.052(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         6776
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0498P)^2^+0.4495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_full    0.790
_reflns_Friedel_fraction_max     0.724
_reflns_number_gt                6453
_reflns_number_total             6776
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00057b2.cif
_cod_data_source_block           nks-ckj-ts-kyn_auto
_cod_depositor_comments
'Adding full bibliography for 7160390--7160394.cif.'
_cod_database_code               7160390
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     'Off-white,block '
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.964
_reflns_odcompleteness_completeness 99.92
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C27(H27), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C30(H30A,H30B)
2.c Aromatic/amide H refined with riding coordinates:
 N4(H4A), N2(H2), C36(H36), C35(H35), C25(H25), C38(H38), C15(H15), C4(H4),
 C7(H7), C33(H33), C6(H6), C16(H16), C19(H19), C22(H22), C26(H26), C34(H34),
 C17(H17), C23(H23), C3(H3), C14(H14)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C29(H29A,H29B,H29C), C10(H10A,H10B,H10C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              72157
_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 2.035
_oxdiff_exptl_absorpt_empirical_full_min 0.490