Synthesis of labionin and avionin precursors <i>via</i> a nitrogen-centred-radical-triggered 1,5-HAT reaction of Tris derivatives.
Yamaguchi, Ayuta; Obiya, Naoki; Arichi, Norihito; Oishi, Shinya; Ohno, Hiroaki; Inuki, Shinsuke; Organic & biomolecular chemistry 22 (2024) 2049–2055; doi:10.1039/d3ob02037a

data_7159810
_publ_section_title
;
 Synthesis of labionin and avionin precursors <i>via</i> a
 nitrogen-centred-radical-triggered 1,5-HAT reaction of Tris derivatives.
;
_journal_issue                   10
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2049
_journal_page_last               2055
_journal_paper_doi               10.1039/d3ob02037a
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C21 H32 N2 O7 S'
_chemical_formula_sum            'C21 H32 N2 O7 S'
_chemical_formula_weight         456.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-29
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2023-12-13 deposited with the CCDC.	2024-01-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.0290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.8319(2)
_cell_length_b                   10.57530(10)
_cell_length_c                   12.59590(10)
_cell_measurement_reflns_used    20801
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.7700
_cell_measurement_theta_min      3.5280
_cell_volume                     2236.56(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_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     39.00  93.00   0.50    0.50    --    5.00  60.00 120.00  108
  2  \w    -76.00 -38.00   0.50    0.50    --    5.00  60.00 150.00   76
  3  \w     27.00  93.00   0.50    0.50    --    5.00  50.00   0.00  132
  4  \w     51.00  94.00   0.50    0.50    --    5.00  60.00  90.00   86
  5  \w    -75.00 -29.00   0.50    0.50    --  -46.70  50.00 150.00   92
  6  \w    -10.00  42.00   0.50    0.50    --  -46.70  15.00 175.90  104
  7  \w     -2.00  42.00   0.50    0.50    --  -46.70  30.00 150.00   88
  8  \w   -136.00 -75.00   0.50    0.50    --  -46.70  20.00 150.00  122
  9  \w    -60.00 -33.00   0.50    0.50    --  -46.70  20.00 150.00   54
 10  \w    -33.00  -8.00   0.50    0.50    --  -97.40  25.00 179.53   50
 11  \w   -138.00-112.00   0.50    0.50    --  -97.40  46.00  -3.22   52
 12  \w   -187.00-153.00   0.50    0.50    --  -97.40  46.00  -3.22   68
 13  \w    -47.00 -21.00   0.50    0.50    --  -97.40  46.00  -3.22   52
 14  \w   -166.00-140.00   0.50    0.50    --  -97.40  41.00  -7.93   52
 15  \w   -125.00 -98.00   0.50    0.50    --  -97.40  25.00 179.53   54
 16  \w    -49.00  -8.00   0.50    0.50    --  -97.40   5.00 175.12   82
 17  \w    -60.00 -10.00   0.50    0.50    --  -97.40  27.00  -7.07  100
 18  \w   -187.00 -64.00   0.50    0.50    --  -97.40   0.00   0.00  246
 19  \w   -125.00 -90.00   0.50    0.50    --  -97.40  27.00  -7.07   70
 20  \w    -52.00  -8.00   0.50    0.50    --  -97.40  43.00 178.01   88
 21  \w    -33.00  -8.00   0.50    0.50    --  -97.40  34.00 178.98   50
 22  \w    -69.00 -27.00   0.50    0.50    --  -97.40  50.00  -7.16   84
 23  \w   -139.00  -8.00   0.50    0.50    --  -97.40  40.00  60.00  262
 24  \w   -185.00 -90.00   0.50    0.50    --  -97.40  10.00   0.00  190
 25  \w    -42.00  -8.00   0.50    0.50    --  -97.40  10.00   0.00   68
 26  \w   -187.00-129.00   0.50    0.50    --  -97.40  27.00  -7.07  116
 27  \w   -187.00 -82.00   0.50    0.50    --  -97.40  50.00  -7.16  210
 28  \w    -48.00  -9.00   0.50    0.50    --  -97.40  40.00  30.00   78
 29  \w    -60.00 -26.00   0.50    0.50    --  -97.40  50.00  90.00   68
 30  \w   -142.00  -8.00   0.50    0.50    --  -97.40   0.00 150.00  268
 31  \w    -33.00  -8.00   0.50    0.50    --  -97.40  41.00  -7.93   50
 32  \w    -43.00  -9.00   0.50    0.50    --  -97.40  13.00 177.55   68
 33  \w   -187.00-161.00   0.50    0.50    --  -97.40  18.00  -6.05   52
 34  \w   -185.00-113.00   0.50    0.50    --  -97.40  43.00 178.01  144
 35  \w    -35.00 -10.00   0.50    0.50    --  -97.40  25.00 175.99   50
 36  \w   -146.00-108.00   0.50    0.50    --  -97.40   5.00 175.12   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0854588000
_diffrn_orient_matrix_UB_12      -0.0278510000
_diffrn_orient_matrix_UB_13      -0.0458815000
_diffrn_orient_matrix_UB_21      0.0308450000
_diffrn_orient_matrix_UB_22      -0.1133480000
_diffrn_orient_matrix_UB_23      -0.0619290000
_diffrn_orient_matrix_UB_31      -0.0128845000
_diffrn_orient_matrix_UB_32      -0.0870900000
_diffrn_orient_matrix_UB_33      0.0953789000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24384
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.202
_diffrn_reflns_theta_min         4.942
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.673
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       plate
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.053
_refine_ls_extinction_coef       0.0063(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         4358
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0483P)^2^+1.2927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0907
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4335
_reflns_number_total             4358
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob02037a2.cif
_cod_data_source_block           exp_231_auto
_cod_depositor_comments
'Adding full bibliography for 7159810--7159811.cif.'
_cod_database_code               7159810
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C21H32N2O7S
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.851
_reflns_odcompleteness_completeness 99.95
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C00B(H00B), C00N(H00N)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00C,H00D), C00I(H00E,H00H), C00R(H00U,H00V)
2.c Aromatic/amide H refined with riding coordinates:
 N00A(H00A), C00F(H00F), C00G(H00G), C00J(H00J), C00P(H00Q)
2.d Idealised Me refined as rotating group:
 C00L(H00I,H00K,H00L), C00O(H00M,H00O,H00P), C00Q(H00R,H00S,H00T), C00S(H00W,
 H00X,H00Y), C00T(H00Z,H,HA), C00V(H00,HB,HC)
2.e Idealised tetrahedral OH refined as rotating group:
 O008(H008)
;
_shelx_res_checksum              93522
_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 1.283
_oxdiff_exptl_absorpt_empirical_full_min 0.728