Chemodivergent C-to-N atom swap from benzofurans to benzisoxazoles and benzoxazoles
Paschke, Ann-Sophie K.; Schiele, Stefanie; Pinard, Camille; Sandrini, Filippo; Morandi, Bill; Chemical Science 16 (2025) 11464–11467; doi:10.1039/D5SC02032H

data_1574726
_publ_section_title
;
 Chemodivergent C-to-N atom swap from benzofurans to benzisoxazoles and
 benzoxazoles
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              11464
_journal_page_last               11467
_journal_paper_doi               10.1039/D5SC02032H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C12 H14 N2 O3'
_chemical_formula_sum            'C12 H14 N2 O3'
_chemical_formula_weight         234.25
_chemical_name_systematic        'tert-butyl benzo[d]isoxazol-5-ylcarbamate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-21 deposited with the CCDC.	2025-05-13 downloaded from the CCDC.
;
_cell_angle_alpha                79.389(3)
_cell_angle_beta                 78.628(3)
_cell_angle_gamma                76.805(3)
_cell_formula_units_Z            2
_cell_length_a                   5.2172(2)
_cell_length_b                   8.9168(3)
_cell_length_c                   13.0925(4)
_cell_measurement_reflns_used    7549
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      72.5990
_cell_measurement_theta_min      3.4520
_cell_volume                     575.14(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.954
_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    -52.00 -26.00   0.50    0.15    --  -14.00 -62.00-101.06   52
  2  \w    -52.00 -26.00   0.50    0.15    --  -14.00 -62.00 -11.51   52
  3  \w    -71.00 -41.00   0.50    0.15    --  -26.00 -55.00  18.74   60
  4  \w    -52.00 -26.00   0.50    0.15    --  -14.00 -62.00  78.29   52
  5  \w    -52.00 -23.00   0.50    0.15    --  -10.00 -61.00 139.47   58
  6  \w    -87.00 -57.00   0.50    0.15    --  -42.00 -55.00 143.19   60
  7  \w    -96.00 -65.00   0.50    0.15    --  -50.00 -52.00 175.60   62
  8  \w    -80.00 -49.00   0.50    0.15    --  -34.00 -52.00  84.51   62
  9  \w    -79.00 -49.00   0.50    0.15    --  -34.00 -55.00  63.35   60
 10  \w    -82.00 -48.00   0.50    0.15    --  -34.00 -44.00 -48.11   68
 11  \w    -85.00 -54.00   0.50    0.15    --  -38.00 -49.00-159.46   62
 12  \w    -94.00 -60.00   0.50    0.15    --  -46.00 -42.00-119.36   68
 13  \w   -113.00 -78.00   0.50    0.15    --  -72.64 -16.00-108.33   70
 14  \w   -124.00 -89.00   0.50    0.60    --  -75.17 -42.00 -80.19   70
 15  \w   -114.00 -83.00   0.50    0.15    --  -70.00 -61.00  48.73   62
 16  \w   -122.00 -91.00   0.50    0.60    --  -75.17 -38.00 -24.92   62
 17  \w   -108.00 -77.00   0.50    0.15    --  -62.00 -54.00 -33.88   62
 18  \w   -109.00 -77.00   0.50    0.15    --  -62.00 -36.00 -83.84   64
 19  \w   -116.00 -85.00   0.50    0.15    --  -70.00 -52.00  51.68   62
 20  \w   -109.00 -78.00   0.50    0.15    --  -62.00 -50.00  83.02   62
 21  \w   -121.00 -90.00   0.50    0.15    --  -74.00 -39.00 129.37   62
 22  \w   -121.00 -93.00   0.50    0.60    --  -75.17 -34.00 159.01   56
 23  \w   -116.00 -90.00   0.50    0.15    --  -72.64 -27.00 127.35   52
 24  \w   -112.00 -83.00   0.50    0.15    --  -66.00 -32.00  -5.85   58
 25  \w   -104.00 -76.00   0.50    0.15    --  -58.00 -33.00-133.81   56
 26  \w   -110.00 -84.00   0.50    0.15    --  -66.00 -27.00-160.35   52
 27  \w   -121.00 -93.00   0.50    0.60    --  -75.17 -33.00-175.86   56
 28  \w   -116.00 -90.00   0.50    0.15    --  -72.64 -26.00-143.05   52
 29  \w   -119.00 -92.00   0.50    0.60    --  -75.17 -26.00 -28.27   54
 30  \w   -115.00 -88.00   0.50    0.15    --  -72.64 -22.00 -64.78   54
 31  \w   -114.00 -87.00   0.50    0.15    --  -72.64 -21.00-174.13   54
 32  \w   -111.00 -84.00   0.50    0.15    --  -70.00 -20.00-138.93   54
 33  \w   -117.00 -90.00   0.50    0.60    --  -75.17 -21.00   6.15   54
 34  \w   -119.00 -92.00   0.50    0.60    --  -75.17 -25.00  35.70   54
 35  \w   -117.00 -89.00   0.50    0.60    --  -75.17 -20.00  55.72   56
 36  \w   -113.00 -86.00   0.50    0.15    --  -70.00 -25.00 150.62   54
 37  \w   -117.00 -89.00   0.50    0.60    --  -75.17 -20.00 133.75   56
 38  \w   -111.00 -81.00   0.50    0.15    --  -70.00 -18.00  76.01   60
 39  \w    -35.00  -8.00   0.50    0.15    --  -54.00  52.00  54.13   54
 40  \w    -38.00 -12.00   0.50    0.15    --  -58.00  54.00 106.27   52
 41  \w    -64.00 -33.00   0.50    0.15    --  -72.64  73.00 135.70   62
 42  \w    -63.00 -33.00   0.50    0.15    --  -72.64  72.00  87.88   60
 43  \w    -35.00  -8.00   0.50    0.15    --  -54.00  52.00 -27.08   54
 44  \w    -35.00  -8.00   0.50    0.15    --  -54.00  52.00 -89.04   54
 45  \w    -35.00  -8.00   0.50    0.15    --  -54.00  52.00-125.97   54
 46  \w    -68.00 -36.00   0.50    0.15    --  -72.64  79.00 -66.74   64
 47  \w    -66.00 -35.00   0.50    0.15    --  -72.64  76.00 -12.63   62
 48  \w    -35.00  -8.00   0.50    0.15    --  -54.00  52.00 152.73   54
 49  \w    -95.00 -25.00   0.50    0.15    --  -69.39 125.00 120.00  140
 50  \w    -95.00 -25.00   0.50    0.15    --  -69.39 125.00 120.00  140
 51  \w    -91.00 -25.00   0.50    0.15    --  -69.39 119.00 140.00  132
 52  \w    -88.00 -22.00   0.50    0.15    --  -66.25 119.00 140.00  132
 53  \w    -31.00  -5.00   0.50    0.15    --  -10.00 117.00 -61.83   52
 54  \w    -99.00 -30.00   0.50    0.60    --  -75.17 121.00-132.30  138
 55  \w    -98.00 -30.00   0.50    0.60    --  -75.17 120.00-117.82  136
 56  \w    -72.00 -35.00   0.50    0.15    --  -72.64  85.00-111.38   74
 57  \w     61.00 105.00   0.50    0.60    --   75.17  11.00 -28.55   88
 58  \w     33.00 100.00   0.50    0.60    --   77.85-125.00-120.00  134
 59  \w     26.00  97.00   0.50    0.15    --   70.78-125.00-120.00  142
 60  \w     33.00 100.00   0.50    0.60    --   77.85-125.00-180.00  134
 61  \w     33.00 100.00   0.50    0.60    --   77.85-125.00   0.00  134
 62  \w     33.00 100.00   0.50    0.60    --   77.85-125.00  30.00  134
 63  \w     33.00 100.00   0.50    0.60    --   77.85-125.00 120.00  134
 64  \w     34.00  98.00   0.50    0.60    --   77.85-119.00  56.00  128
 65  \w     33.00 100.00   0.50    0.60    --   77.85-125.00  30.00  134
 66  \w     24.00  90.00   0.50    0.15    --   67.93-119.00  56.00  132
 67  \w     27.00  93.00   0.50    0.15    --   70.78-119.00  56.00  132
 68  \w     37.00  85.00   0.50    0.60    --   77.85 -95.00  60.00   96
 69  \w     37.00  85.00   0.50    0.60    --   77.85 -95.00 150.00   96
 70  \w     37.00  85.00   0.50    0.60    --   77.85 -95.00  90.00   96
 71  \w     37.00  85.00   0.50    0.60    --   77.85 -95.00-180.00   96
 72  \w     33.00 100.00   0.50    0.60    --   77.85-125.00-180.00  134
 73  \w     37.00  85.00   0.50    0.60    --   77.85 -95.00-120.00   96
 74  \w     89.00 115.00   0.50    0.15    --   72.89  22.00 147.77   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2104546000
_diffrn_orient_matrix_UB_12      -0.1489454000
_diffrn_orient_matrix_UB_13      -0.0181174000
_diffrn_orient_matrix_UB_21      -0.0467698000
_diffrn_orient_matrix_UB_22      -0.0595958000
_diffrn_orient_matrix_UB_23      0.1189906000
_diffrn_orient_matrix_UB_31      -0.2190635000
_diffrn_orient_matrix_UB_32      -0.0802357000
_diffrn_orient_matrix_UB_33      -0.0152139000
_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  0.0484
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            13801
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.391
_diffrn_reflns_theta_min         3.481
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.737
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       plate
_exptl_crystal_F_000             248
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     160
_refine_ls_number_reflns         2244
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0873P)^2^+0.1396P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1333
_refine_ls_wR_factor_ref         0.1389
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1876
_reflns_number_total             2244
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02032h2.cif
_cod_data_source_block           bm301124_2_1
_cod_depositor_comments
'Adding full bibliography for 1574726--1574728.cif.'
_cod_database_code               1574726
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C12H14N2O3
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.860
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C12(H12), C11(H11), C9(H9)
3.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              94299
_olex2_date_sample_submission    2024-11-26
_olex2_submission_original_sample_id bm301124_2_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.372
_oxdiff_exptl_absorpt_empirical_full_min 0.404