Solvent-controlled, chemodivergent oxidative anionic Fries rearrangement of <i>O</i>-aryl carbamates under aerobic conditions.
Gnavi, Riccardo; De Nardi, Federica; Meazzo, Carolina; Ghinato, Simone; Grimaldi, Ettore; Maranzana, Andrea; Prandi, Cristina; Blangetti, Marco; Chemical science 17 (2026) 5701–5711; doi:10.1039/d5sc09227b

data_1576893
_publ_section_title
;
 Solvent-controlled, chemodivergent oxidative anionic Fries rearrangement
 of <i>O</i>-aryl carbamates under aerobic conditions.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              5701
_journal_page_last               5711
_journal_paper_doi               10.1039/d5sc09227b
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C15 H23 N O3'
_chemical_formula_sum            'C15 H23 N O3'
_chemical_formula_weight         265.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-04-07
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-07-23 deposited with the CCDC.	2026-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.224(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4288(5)
_cell_length_b                   12.6625(7)
_cell_length_c                   13.1745(7)
_cell_measurement_reflns_used    6306
_cell_measurement_temperature    298
_cell_measurement_theta_max      26.3920
_cell_measurement_theta_min      3.8660
_cell_volume                     1566.40(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1990
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.927
_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    -41.00   3.00   1.00   50.00    --   -9.89  69.00 -32.78   44
  2  \w    -13.00  77.00   1.00   50.00    --   11.30  37.00  90.00   90
  3  \w    -37.00  39.00   1.00   50.00    --   11.30 -57.00 120.00   76
  4  \w    -35.00  -9.00   1.00   50.00    --   11.30 -57.00 -90.00   26
  5  \w      6.00  39.00   1.00   50.00    --   11.30 -57.00 -90.00   33
  6  \w    -61.00  39.00   1.00   50.00    --   11.30 -57.00  30.00  100
  7  \w     -2.00  84.00   1.00   50.00    --   11.30  57.00 -60.00   86
  8  \w    -36.00  39.00   1.00   50.00    --   11.30 -57.00-150.00   75
  9  \w    -19.00  56.00   1.00   50.00    --   11.30  69.00 170.58   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0135349000
_diffrn_orient_matrix_UB_12      -0.0256665000
_diffrn_orient_matrix_UB_13      -0.0477683000
_diffrn_orient_matrix_UB_21      -0.0588722000
_diffrn_orient_matrix_UB_22      -0.0265803000
_diffrn_orient_matrix_UB_23      0.0181876000
_diffrn_orient_matrix_UB_31      -0.0453389000
_diffrn_orient_matrix_UB_32      0.0421290000
_diffrn_orient_matrix_UB_33      -0.0175787000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0404
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25743
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.650
_diffrn_reflns_theta_min         3.498
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87541
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.125
_exptl_crystal_description       plate
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.155
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         4101
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1034
_refine_ls_R_factor_gt           0.0617
_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^)+(0.0719P)^2^+0.3837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1512
_refine_ls_wR_factor_ref         0.1721
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2591
_reflns_number_total             4101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09227b2.cif
_cod_data_source_block           preex1_auto
_cod_original_cell_volume        1566.41(15)
_cod_database_code               1576893
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.992
_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, All O(H) groups
2. Rigid bond restraints
 C11, C10, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C11 \\sim C10 \\sim C12: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
4.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C13(H13)
4.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C4(H4), C3(H3)
4.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C15(H15A,H15B,
 H15C), C11(H11A,H11B,H11C)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              15350
_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 1.196
_oxdiff_exptl_absorpt_empirical_full_min 0.842