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_1574727
_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         'C13 H15 N O3'
_chemical_formula_sum            'C13 H15 N O3'
_chemical_formula_weight         233.26
_chemical_name_systematic        'tert-butyl benzofuran-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                102.318(2)
_cell_angle_beta                 100.925(2)
_cell_angle_gamma                94.671(2)
_cell_formula_units_Z            2
_cell_length_a                   5.2939(2)
_cell_length_b                   10.5894(3)
_cell_length_c                   11.1328(3)
_cell_measurement_reflns_used    8271
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      73.9040
_cell_measurement_theta_min      4.1310
_cell_volume                     593.83(3)
_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 0.990
_diffrn_measured_fraction_theta_max 0.946
_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    -28.00  -3.00   0.50    0.20    --  -50.00  47.00 -64.73   50
  2  \w    -28.00  -3.00   0.50    0.20    --  -50.00  47.00  55.07   50
  3  \w    -24.00   1.00   0.50    0.20    --  -46.00  45.00 108.07   50
  4  \w    -38.00 -13.00   0.50    0.20    --  -58.00  54.00 144.60   50
  5  \w    -57.00 -32.00   0.50    0.20    --  -72.64  68.00 171.82   50
  6  \w    -35.00 -10.00   0.50    0.20    --  -54.00  52.00 152.71   50
  7  \w    -34.00  -9.00   0.50    0.20    --  -54.00  52.00  86.33   50
  8  \w    -35.00 -10.00   0.50    0.20    --  -54.00  52.00  40.22   50
  9  \w    -35.00  -9.00   0.50    0.20    --  -54.00  52.00  12.70   52
 10  \w    -33.00  -7.00   0.50    0.20    --  -54.00  51.00 -86.35   52
 11  \w    -32.00  -7.00   0.50    0.20    --  -54.00  51.00-140.63   50
 12  \w    -72.00 -26.00   0.50    0.20    --  -66.25 125.00-150.00   92
 13  \w    -75.00 -38.00   0.50    0.20    --  -69.39 125.00-180.00   74
 14  \w    -67.00 -27.00   0.50    0.20    --  -69.39 125.00 -90.00   80
 15  \w    -64.00 -39.00   0.50    0.80    --  -75.17 121.00-146.27   50
 16  \w    -57.00 -25.00   0.50    0.20    --  -69.39 125.00   0.00   64
 17  \w    -88.00 -62.00   0.50    0.20    --  -69.39 125.00   0.00   52
 18  \w    -56.00 -27.00   0.50    0.20    --  -69.39 125.00 150.00   58
 19  \w    -23.00   2.00   0.50    0.20    --  -26.00  81.00 110.04   50
 20  \w     61.00  86.00   0.50    0.20    --   46.00  55.00 153.09   50
 21  \w     68.00  97.00   0.50    0.80    --   75.17  11.00 166.00   58
 22  \w     79.00 104.00   0.50    0.20    --   72.89  11.00   4.74   50
 23  \w     61.00  86.00   0.50    0.20    --   46.00  54.00 -38.49   50
 24  \w     61.00  86.00   0.50    0.20    --   46.00  55.00 -61.34   50
 25  \w     73.00 103.00   0.50    0.80    --   75.17  11.00-109.47   60
 26  \w     67.00 112.00   0.50    0.20    --   72.89  14.00 -72.35   90
 27  \w    -28.00  -3.00   0.50    0.20    --    6.00 -73.00 134.27   50
 28  \w     24.00  50.00   0.50    0.20    --   67.93-125.00 150.00   52
 29  \w     63.00  89.00   0.50    0.20    --   67.93-125.00 150.00   52
 30  \w     26.00  61.00   0.50    0.20    --   70.78-125.00  30.00   70
 31  \w     69.00  96.00   0.50    0.20    --   70.78-125.00  30.00   54
 32  \w     74.00 100.00   0.50    0.80    --   77.85-125.00  30.00   52
 33  \w     29.00  55.00   0.50    0.20    --   70.78-125.00 -90.00   52
 34  \w     29.00  59.00   0.50    0.20    --   67.93-125.00-150.00   60
 35  \w     63.00  89.00   0.50    0.20    --   67.93-125.00-150.00   52
 36  \w     72.00  97.00   0.50    0.20    --   70.78-125.00 -90.00   50
 37  \w     42.00  68.00   0.50    0.80    --   77.85-125.00  30.00   52
 38  \w     72.00  99.00   0.50    0.80    --   77.85-125.00  60.00   54
 39  \w     75.00 100.00   0.50    0.80    --   77.85-125.00 150.00   50
 40  \w     41.00  67.00   0.50    0.80    --   77.85-125.00 150.00   52
 41  \w     35.00  99.00   0.50    0.80    --   77.85-125.00 120.00  128
 42  \w     36.00  67.00   0.50    0.80    --   77.85-125.00  60.00   62
 43  \w     34.00  64.00   0.50    0.20    --   67.93 -95.00  60.00   60
 44  \w     34.00  70.00   0.50    0.20    --   70.78 -95.00 -30.00   72
 45  \w     34.00 100.00   0.50    0.80    --   77.85-125.00 -30.00  132
 46  \w     35.00 100.00   0.50    0.80    --   77.85-125.00-120.00  130
 47  \w     42.00  98.00   0.50    0.80    --   77.85-125.00-180.00  112
 48  \w    -42.00 -17.00   0.50    0.20    --   -2.00 -67.00  -3.68   50
 49  \w    -50.00 -25.00   0.50    0.20    --  -10.00 -63.00 -79.64   50
 50  \w    -47.00 -22.00   0.50    0.20    --   -6.00 -65.00 -51.54   50
 51  \w    -52.00 -27.00   0.50    0.20    --  -10.00 -61.00-160.12   50
 52  \w    -52.00 -26.00   0.50    0.20    --  -14.00 -62.00  48.73   52
 53  \w    -52.00 -27.00   0.50    0.20    --  -14.00 -62.00  93.24   50
 54  \w    -50.00 -25.00   0.50    0.20    --  -10.00 -63.00 120.66   50
 55  \w    -51.00 -26.00   0.50    0.20    --  -14.00 -62.00 147.23   50
 56  \w    -95.00 -70.00   0.50    0.20    --  -50.00 -55.00  75.15   50
 57  \w    -53.00 -28.00   0.50    0.20    --  -14.00 -59.00  17.92   50
 58  \w    -67.00 -41.00   0.50    0.20    --  -26.00 -55.00 -27.03   52
 59  \w    -53.00 -28.00   0.50    0.20    --  -14.00 -59.00-123.43   50
 60  \w    -80.00 -54.00   0.50    0.20    --  -38.00 -54.00-170.65   52
 61  \w    -90.00 -64.00   0.50    0.20    --  -46.00 -54.00-136.59   52
 62  \w    -92.00 -66.00   0.50    0.20    --  -50.00 -53.00 -33.18   52
 63  \w    -75.00 -49.00   0.50    0.20    --  -34.00 -53.00 -60.37   52
 64  \w    -90.00 -65.00   0.50    0.20    --  -50.00 -54.00  50.52   50
 65  \w    -80.00 -54.00   0.50    0.20    --  -38.00 -52.00  54.14   52
 66  \w    -63.00 -38.00   0.50    0.20    --  -22.00 -53.00  72.35   50
 67  \w    -64.00 -39.00   0.50    0.20    --  -18.00 -54.00 125.39   50
 68  \w    -78.00 -53.00   0.50    0.20    --  -38.00 -52.00  73.53   50
 69  \w    -90.00 -64.00   0.50    0.20    --  -46.00 -51.00 169.85   52
 70  \w    -82.00 -57.00   0.50    0.20    --  -38.00 -51.00  25.55   50
 71  \w    -74.00 -48.00   0.50    0.20    --  -30.00 -51.00 -12.46   52
 72  \w    -90.00 -65.00   0.50    0.20    --  -50.00 -52.00 -77.65   50
 73  \w    -87.00 -61.00   0.50    0.20    --  -46.00 -52.00 -70.71   52
 74  \w    -67.00 -41.00   0.50    0.20    --  -26.00 -52.00-168.27   52
 75  \w    -85.00 -59.00   0.50    0.20    --  -42.00 -49.00-118.05   52
 76  \w    -90.00 -65.00   0.50    0.20    --  -50.00 -47.00 -25.92   50
 77  \w    -83.00 -57.00   0.50    0.20    --  -38.00 -48.00 106.61   52
 78  \w   -114.00 -86.00   0.50    0.20    --  -72.64 -67.00  69.15   56
 79  \w   -114.00 -89.00   0.50    0.20    --  -72.64 -67.00  32.57   50
 80  \w   -115.00 -85.00   0.50    0.20    --  -72.64 -66.00  84.14   60
 81  \w   -109.00 -84.00   0.50    0.20    --  -72.64 -65.00 139.33   50
 82  \w   -109.00 -84.00   0.50    0.20    --  -72.64 -65.00 155.76   50
 83  \w   -110.00 -85.00   0.50    0.20    --  -72.64 -64.00 -84.53   50
 84  \w   -117.00 -86.00   0.50    0.80    --  -75.17 -67.00 -72.22   62
 85  \w   -113.00 -87.00   0.50    0.20    --  -72.64 -65.00-110.33   52
 86  \w   -114.00 -88.00   0.50    0.20    --  -72.64 -67.00-117.85   52
 87  \w   -111.00 -85.00   0.50    0.20    --  -72.64 -64.00 -96.25   52
 88  \w   -110.00 -85.00   0.50    0.20    --  -72.64 -64.00 -57.64   50
 89  \w   -115.00 -90.00   0.50    0.80    --  -75.17 -63.00-133.16   50
 90  \w   -108.00 -83.00   0.50    0.20    --  -70.00 -63.00-153.83   50
 91  \w   -114.00 -88.00   0.50    0.20    --  -72.64 -64.00 -43.87   52
 92  \w   -115.00 -90.00   0.50    0.20    --  -72.64 -61.00  -4.51   50
 93  \w   -112.00 -87.00   0.50    0.20    --  -74.00 -61.00   8.77   50
 94  \w   -110.00 -80.00   0.50    0.20    --  -66.00 -59.00  32.98   60
 95  \w   -115.00 -87.00   0.50    0.20    --  -72.64 -61.00  52.66   56
 96  \w   -114.00 -86.00   0.50    0.20    --  -74.00 -64.00 100.50   56
 97  \w   -110.00 -85.00   0.50    0.20    --  -72.64 -64.00 119.83   50
 98  \w    -94.00 -69.00   0.50    0.20    --  -54.00 -54.00 149.54   50
 99  \w   -103.00 -78.00   0.50    0.20    --  -62.00 -50.00 162.11   50
100  \w    -94.00 -69.00   0.50    0.20    --  -54.00 -54.00  29.46   50
101  \w   -104.00 -78.00   0.50    0.20    --  -62.00 -46.00 127.80   52
102  \w    -98.00 -72.00   0.50    0.20    --  -54.00 -55.00   9.63   52
103  \w   -106.00 -81.00   0.50    0.20    --  -62.00 -50.00 -44.42   50
104  \w    -96.00 -71.00   0.50    0.20    --  -54.00 -54.00-155.03   50
105  \w   -115.00 -90.00   0.50    0.80    --  -75.17 -21.00-132.58   50
106  \w   -117.00 -92.00   0.50    0.80    --  -75.17 -21.00 -39.15   50
107  \w   -102.00 -76.00   0.50    0.20    --  -72.64 -14.00-115.30   52
108  \w   -107.00 -81.00   0.50    0.20    --  -70.00 -18.00 -27.29   52
109  \w   -102.00 -75.00   0.50    0.20    --  -72.64 -11.00 -83.35   54
110  \w   -109.00 -70.00   0.50    0.80    --  -75.17 -11.00   0.76   78
111  \w   -110.00 -84.00   0.50    0.20    --  -70.00 -20.00  72.04   52
112  \w   -104.00 -72.00   0.50    0.20    --  -66.00 -15.00  88.83   64
113  \w   -111.00 -84.00   0.50    0.20    --  -70.00 -17.00 129.06   54
;
_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      0.2576964000
_diffrn_orient_matrix_UB_12      0.0654787000
_diffrn_orient_matrix_UB_13      0.0897081000
_diffrn_orient_matrix_UB_21      -0.1008022000
_diffrn_orient_matrix_UB_22      0.1335605000
_diffrn_orient_matrix_UB_23      0.0113222000
_diffrn_orient_matrix_UB_31      -0.1127504000
_diffrn_orient_matrix_UB_32      -0.0202932000
_diffrn_orient_matrix_UB_33      0.1132914000
_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  0.0559
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            15691
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.576
_diffrn_reflns_theta_min         4.160
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.762
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.739
_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    1.305
_exptl_crystal_description       plank
_exptl_crystal_F_000             248
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.297
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     160
_refine_ls_number_reflns         2304
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0425
_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^)+(0.0729P)^2^+0.1025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1197
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1941
_reflns_number_total             2304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02032h2.cif
_cod_data_source_block           bm281124_1_1
_cod_depositor_comments
'Adding full bibliography for 1574726--1574728.cif.'
_cod_database_code               1574727
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C13H15NO3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.881
_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:
 C8(H8), C2(H2), C6(H6), C3(H3), C5(H5)
3.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              69654
_olex2_date_sample_data_collection 2024-11-26
_olex2_date_sample_submission    2024-11-26
_olex2_submission_original_sample_id bm281124_1_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 3.733
_oxdiff_exptl_absorpt_empirical_full_min 0.422