Selective modification of tryptophan in polypeptides <i>via</i> C-N coupling with azoles using <i>in situ</i>-generated iodine-based oxidants in aqueous media.
Watanabe, Shunsuke; Wada, Yuki; Kawano, Masaki; Higashibayashi, Shuhei; Sugai, Takeshi; Hanaya, Kengo; Chemical communications (Cambridge, England)  (2023) –; doi:10.1039/d3cc03731b

data_7132210
_publ_section_title
;
 Selective modification of tryptophan in polypeptides <i>via</i> C-N
 coupling with azoles using <i>in situ</i>-generated iodine-based oxidants
 in aqueous media.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d3cc03731b
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H17 N5 O3'
_chemical_formula_sum            'C16 H17 N5 O3'
_chemical_formula_weight         327.34
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-29 deposited with the CCDC.	2023-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.9580(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.78319(6)
_cell_length_b                   10.61767(7)
_cell_length_c                   9.51916(6)
_cell_measurement_reflns_used    24799
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      75.5420
_cell_measurement_theta_min      5.1020
_cell_volume                     804.830(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -74.00 -30.00   0.50    0.06    -- -102.00  61.00-180.00   88
  2  \w    -74.00 -30.00   0.50    0.06    -- -102.00  61.00 -30.00   88
  3  \w   -124.00 -30.00   0.50    0.06    -- -102.00  77.00  60.00  188
  4  \w     -6.00  26.00   0.50    0.06    --  -48.44  19.00  30.00   64
  5  \w     27.00 121.00   0.50    0.06    --   48.44  77.00   0.00  188
  6  \w     27.00 121.00   0.50    0.06    --   48.44  77.00  30.00  188
  7  \w     27.00 121.00   0.50    0.06    --   48.44  77.00 -60.00  188
  8  \w     27.00 121.00   0.50    0.06    --   48.44  77.00 -30.00  188
  9  \w     39.00 121.00   0.50    0.06    --   48.44  37.00  30.00  164
 10  \w     39.00 123.00   0.50    0.06    --   48.44  19.00 -30.00  168
 11  \w     38.00 123.00   0.50    0.06    --   48.44  13.00-101.00  170
 12  \w     81.00 174.00   0.50    0.06    --  102.75  77.00-120.00  186
 13  \w     81.00 174.00   0.50    0.06    --  102.75  77.00 -90.00  186
 14  \w     81.00 174.00   0.50    0.06    --  102.75  77.00 -60.00  186
 15  \w    115.00 141.00   0.50    0.06    --  102.75  77.00   0.00   52
 16  \w     81.00 106.00   0.50    0.06    --  102.75  77.00   0.00   50
 17  \w     81.00 165.00   0.50    0.06    --  102.75  77.00  30.00  168
 18  \w     88.00 174.00   0.50    0.06    --  102.75  61.00 -30.00  172
 19  \w     90.00 117.00   0.50    0.06    --  102.75  61.00 -90.00   54
 20  \w     92.00 174.00   0.50    0.06    --  102.75  45.00 -30.00  164
 21  \w     92.00 170.00   0.50    0.06    --  102.75  13.00-101.00  156
 22  \w     31.00  79.00   0.50    0.06    --  102.75 -61.00 -60.00   96
 23  \w     31.00 106.00   0.50    0.06    --  102.75 -94.00 -90.00  150
 24  \w     32.00  76.00   0.50    0.06    --  102.75 -61.00-150.00   88
 25  \w     31.00 106.00   0.50    0.06    --  102.75 -94.00-150.00  150
 26  \w     19.00  93.00   0.50    0.06    --   48.44-125.00-120.00  148
 27  \w     32.00 103.00   0.50    0.06    --  102.75 -94.00-180.00  142
 28  \w     31.00 106.00   0.50    0.06    --  102.75 -94.00 -60.00  150
 29  \w     34.00 111.00   0.50    0.06    --  102.75-125.00   0.00  154
 30  \w     31.00 106.00   0.50    0.06    --  102.75 -94.00  90.00  150
 31  \w   -121.00 -37.00   0.50    0.06    --  -48.44 -13.00  86.00  168
 32  \w   -121.00 -37.00   0.50    0.06    --  -48.44 -37.00  30.00  168
 33  \w   -119.00 -34.00   0.50    0.06    --  -48.44 -57.00   0.00  170
 34  \w   -118.00 -32.00   0.50    0.06    -- -102.00 134.00 -55.95  172
 35  \w   -111.00 -33.00   0.50    0.06    -- -102.00 125.00 -30.00  156
 36  \w   -165.00 -91.00   0.50    0.06    -- -102.00 -13.00  86.00  148
 37  \w   -174.00 -80.00   0.50    0.06    -- -102.00 -77.00  67.32  188
 38  \w   -174.00 -80.00   0.50    0.06    -- -102.00 -77.00  30.00  188
 39  \w   -174.00 -81.00   0.50    0.06    -- -102.00 -76.00  93.13  186
 40  \w   -174.00 -80.00   0.50    0.06    -- -102.00 -77.00   0.00  188
 41  \w   -174.00 -82.00   0.50    0.06    -- -102.00 -73.00   8.29  184
 42  \w   -174.00 -81.00   0.50    0.06    -- -102.00 -74.00  18.42  186
 43  \w   -174.00 -83.00   0.50    0.06    -- -102.00 -69.00  31.12  182
 44  \w   -174.00 -85.00   0.50    0.06    -- -102.00 -64.00  63.62  178
 45  \w   -174.00 -80.00   0.50    0.06    -- -102.00 -77.00 -45.16  188
 46  \w   -174.00 -87.00   0.50    0.06    -- -102.00 -61.00 -60.00  174
 47  \w   -174.00 -80.00   0.50    0.06    -- -102.00 -77.00 -30.00  188
 48  \w   -174.00 -81.00   0.50    0.06    -- -102.00 -74.00 -19.18  186
 49  \w   -174.00 -88.00   0.50    0.06    -- -102.00 -57.00 -40.76  172
 50  \w   -174.00 -91.00   0.50    0.06    -- -102.00 -45.00 -30.00  166
 51  \w   -174.00 -87.00   0.50    0.06    -- -102.00 -59.00  33.43  174
 52  \w   -174.00 -87.00   0.50    0.06    -- -102.00 -61.00  30.00  174
 53  \w   -174.00 -87.00   0.50    0.06    -- -102.00 -59.00  53.62  174
 54  \w   -169.00 -91.00   0.50    0.06    -- -102.00 -15.00-120.00  156
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0027528000
_diffrn_orient_matrix_UB_12      0.0252874000
_diffrn_orient_matrix_UB_13      0.1604453000
_diffrn_orient_matrix_UB_21      0.1934365000
_diffrn_orient_matrix_UB_22      -0.0032698000
_diffrn_orient_matrix_UB_23      0.0736496000
_diffrn_orient_matrix_UB_31      0.0038912000
_diffrn_orient_matrix_UB_32      0.1427937000
_diffrn_orient_matrix_UB_33      -0.0266954000
_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  0.0278
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            26347
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.621
_diffrn_reflns_theta_min         5.125
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.802
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61432
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (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    1.351
_exptl_crystal_description       block
_exptl_crystal_F_000             344
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethyl acetate and hexane.'
_exptl_crystal_size_max          0.72
_exptl_crystal_size_mid          0.52
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.132
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1400 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3170
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0266
_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^)+(0.0422P)^2^+0.1230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0672
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    0.928
_reflns_Friedel_fraction_max     0.896
_reflns_number_gt                3159
_reflns_number_total             3170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03731b2.cif
_cod_data_source_block
N-acetyl-2-(1H-1_2_3-triazol-1-yl)-L-tryptophan_methyl_ester
_cod_original_cell_volume        804.830(10)
_cod_database_code               7132210
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNO
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.596
_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:
 C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), N7(H7), C9(H9), C10(H10), C11(H11), C12(H12), N21(H21)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              43158
_shelx_hkl_checksum              50457
_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 1.673
_oxdiff_exptl_absorpt_empirical_full_min 0.791