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_7160394
_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(C20 H27 N3 O7)'
_chemical_formula_sum            'C40 H54 N6 O14'
_chemical_formula_weight         842.89
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-04
_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                65.827(2)
_cell_angle_beta                 69.312(3)
_cell_angle_gamma                63.964(3)
_cell_formula_units_Z            1
_cell_length_a                   9.6582(4)
_cell_length_b                   10.8402(3)
_cell_length_c                   12.8768(3)
_cell_measurement_reflns_used    12027
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      77.1810
_cell_measurement_theta_min      3.8000
_cell_volume                     1080.08(7)
_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      100.01(11)
_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 0.974
_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   -102.00 -33.00   0.50    1.15    --  -38.50 -48.00-107.00  138
  2  \w     44.00 113.00   0.50    1.15    --   48.81  48.00  40.00  138
  3  \w    -15.00  54.00   0.50    1.15    --   48.81 -48.00-107.00  138
  4  \w     43.00 112.00   0.50    4.43    --  106.83 -48.00-107.00  138
  5  \w    102.00 171.00   0.50    4.43    --  106.83  48.00  40.00  138
  6  \w   -105.00 -35.00   0.50    1.15    --  -38.50 -38.00   0.00  140
  7  \w    -44.00  26.00   0.50    1.15    --  -38.50  48.00  40.00  140
  8  \w   -101.00 -26.00   0.50    1.15    --  -38.50 -60.00 176.56  150
  9  \w    -42.00  28.00   0.50    1.15    --  -38.50  38.00 -30.00  140
 10  \w     28.00  98.00   0.50    1.15    --   48.81-125.00-120.00  140
 11  \w    -14.00  60.00   0.50    1.15    --   48.81 -57.00 120.00  148
 12  \w      7.00  84.00   0.50    1.15    --   48.81 -99.00  90.00  154
 13  \w    102.00 171.00   0.50    4.43    --  106.83  45.00   0.00  138
 14  \w     39.00 106.00   0.50    4.43    --  106.83 -94.00  30.00  134
 15  \w     44.00 112.00   0.50    4.43    --  106.83-125.00-120.00  136
 16  \w     39.00 110.00   0.50    4.43    --  106.83 -30.00-180.00  142
 17  \w    103.00 171.00   0.50    4.43    --  106.83  77.00 150.00  136
 18  \w     39.00 106.00   0.50    4.43    --  106.83 -94.00 -30.00  134
 19  \w     44.00 112.00   0.50    4.43    --  106.83-125.00 150.00  136
 20  \w     97.00 170.00   0.50    4.43    --  106.83 125.00 -30.00  146
 21  \w     44.00 124.00   0.50    4.43    --  106.83-140.00 -70.49  160
 22  \w     44.00 112.00   0.50    4.43    --  106.83-125.00 -30.00  136
 23  \w     44.00 112.00   0.50    4.43    --  106.83-125.00  90.00  136
 24  \w     39.00 106.00   0.50    4.43    --  106.83 -94.00-180.00  134
 25  \w     42.00 111.00   0.50    4.43    --  106.83 -45.00  90.00  138
 26  \w    102.00 171.00   0.50    4.43    --  106.83  45.00 -90.00  138
 27  \w     90.00 170.00   0.50    4.43    --  106.83  67.00  -0.30  160
 28  \w    103.00 171.00   0.50    4.43    --  106.83  77.00 120.00  136
 29  \w     43.00 130.00   0.50    4.43    --  106.83 -77.00 -30.00  174
 30  \w     39.00 106.00   0.50    4.43    --  106.83 -94.00 120.00  134
 31  \w    103.00 171.00   0.50    4.43    --  106.83  77.00 -60.00  136
 32  \w    103.00 171.00   0.50    4.43    --  106.83  77.00  60.00  136
 33  \w     41.00  97.00   0.50    4.43    --  106.83 -30.00   0.00  112
 34  \w     41.00 108.00   0.50    4.43    --  106.83-104.00 -89.97  134
 35  \w    106.00 162.00   0.50    4.43    --  106.83  30.00 -60.00  112
 36  \w     51.00 114.00   0.50    4.43    --  106.83 -61.00  30.00  126
;
_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      -0.1447248000
_diffrn_orient_matrix_UB_12      -0.0112979000
_diffrn_orient_matrix_UB_13      0.0998443000
_diffrn_orient_matrix_UB_21      -0.0939199000
_diffrn_orient_matrix_UB_22      0.0295331000
_diffrn_orient_matrix_UB_23      -0.0876985000
_diffrn_orient_matrix_UB_31      0.0568056000
_diffrn_orient_matrix_UB_32      -0.1629114000
_diffrn_orient_matrix_UB_33      0.0185478000
_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  0.0562
_diffrn_reflns_av_unetI/netI     0.0592
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            16820
_diffrn_reflns_point_group_measured_fraction_full 0.700
_diffrn_reflns_point_group_measured_fraction_max 0.672
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.791
_diffrn_reflns_theta_min         3.850
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.826
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77559
_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 brownish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.629
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 1563 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.979
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     551
_refine_ls_number_reflns         6208
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0675
_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^)+(0.1301P)^2^+0.9130P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1806
_refine_ls_wR_factor_ref         0.1848
_reflns_Friedel_coverage         0.380
_reflns_Friedel_fraction_full    0.403
_reflns_Friedel_fraction_max     0.370
_reflns_number_gt                6020
_reflns_number_total             6208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00057b2.cif
_cod_data_source_block           nks-ckj-boc-ala-kyn_auto
_cod_depositor_comments
'Adding full bibliography for 7160390--7160394.cif.'
_cod_database_code               7160394
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C N H O '
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.992
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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:
 C10(H10), C16(H16), C14(H14), C018(H018)
2.b Secondary CH2 refined with riding coordinates:
 C011(H01G,H01H), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N5(H5A), N1(H1), N3(H3), N4(H4A), N6(H6A), C00S(H00S), C00U(H00U),
 C014(H014), C015(H015), C4(H4), C3(H3A), C01A(H01I), C6(H6), C5(H5), C1(H1A)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C12(H12A,H12B,H12C), C01H(H01J,H01K,H01L), C01I(H01M,
 H01N,H01O), C17(H17A,H17B,H17C), C01K(H01P,H01Q,H01R), C01L(H01A,H01B,H01C),
 C01M(H01D,H01E,H01F), C01N(H01S,H01T,H01U), C01O(H01V,H01W,H01X)
;
_shelx_res_checksum              81918
_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 1.749
_oxdiff_exptl_absorpt_empirical_full_min 0.436