<i>O</i>-Aryl carbamates of 2-substituted piperidines: anionic Fries rearrangement and kinetic resolution by lithiation.
Marra, Francesco; Morelli, Fabrizio; De Nardi, Federica; Priola, Emanuele; Coldham, Iain; Blangetti, Marco; Organic & biomolecular chemistry 23 (2025) 8029–8038; doi:10.1039/d5ob01049g

data_7160696
_publ_section_title
;
 <i>O</i>-Aryl carbamates of 2-substituted piperidines: anionic Fries
 rearrangement and kinetic resolution by lithiation.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8029
_journal_page_last               8038
_journal_paper_doi               10.1039/d5ob01049g
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C19 H21 N O2'
_chemical_formula_sum            'C19 H21 N O2'
_chemical_formula_weight         295.37
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-04-17
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-04-17 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.979(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7494(4)
_cell_length_b                   11.1404(3)
_cell_length_c                   14.0361(5)
_cell_measurement_reflns_used    6744
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.2750
_cell_measurement_theta_min      4.5620
_cell_volume                     1615.92(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 5.1990
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     22.00 113.00   1.00   15.00    --   42.89  57.00-150.00   91
  2  \w     -6.00  63.00   1.00   15.00    --   42.89 -57.00 -90.00   69
  3  \w    -29.00  70.00   1.00   15.00    --   42.89 -57.00  60.00   99
  4  \w     51.00 123.00   1.00   15.00    --   92.50 -70.00 -81.73   72
  5  \w    134.00 177.00   1.00   15.00    --   92.50   0.00   0.00   43
  6  \w     19.00 122.00   1.00   15.00    --   92.50 -69.00  39.96  103
  7  \w     24.00  50.00   1.00   15.00    --   92.50   0.00   0.00   26
  8  \w     30.00  69.00   1.00   15.00    --   92.50 -70.00 -50.63   39
  9  \w     55.00 106.00   1.00   15.00    --   92.50 -30.00 -90.00   51
 10  \w     80.00 105.00   1.00   15.00    --   92.50 -45.00  60.00   25
 11  \w     41.00  67.00   1.00   15.00    --   92.50 -45.00-180.00   26
 12  \w     58.00 103.00   1.00   15.00    --   92.50 -70.00 123.20   45
 13  \w     19.00  58.00   1.00   15.00    --   92.50 -69.00  -9.24   39
 14  \w     71.00 118.00   1.00   15.00    --   92.50 -69.00  -9.24   47
 15  \w     64.00 146.00   1.00   15.00    --   92.50  30.00 120.00   82
 16  \w     62.00  87.00   1.00   15.00    --   92.50 -70.00 161.75   25
 17  \w     16.00 113.00   1.00   15.00    --   92.50 -30.00-180.00   97
 18  \w     89.00 115.00   1.00   15.00    --   92.50 -70.00 -50.63   26
 19  \w     65.00  91.00   1.00   15.00    --   92.50 -30.00  60.00   26
 20  \w     95.00 120.00   1.00   15.00    --   92.50 -30.00  60.00   25
 21  \w     25.00  50.00   1.00   15.00    --   92.50 -70.00  69.41   25
 22  \w     79.00 104.00   1.00   15.00    --   92.50 -70.00  69.41   25
 23  \w     67.00 102.00   1.00   15.00    --   92.50 -70.00-139.94   35
 24  \w     75.00 101.00   1.00   15.00    --   92.50 -45.00-180.00   26
 25  \w     41.00  93.00   1.00   15.00    --   92.50  15.00  30.00   52
 26  \w    104.00 148.00   1.00   15.00    --   92.50  15.00  30.00   44
 27  \w    126.00 161.00   1.00   15.00    --   92.50  61.00-150.00   35
 28  \w     31.00 121.00   1.00   15.00    --   92.50 -61.00-180.00   90
 29  \w     64.00  90.00   1.00   15.00    --   92.50 -70.00  17.55   26
 30  \w     22.00  60.00   1.00   15.00    --   92.50 -70.00 161.75   38
 31  \w     70.00  95.00   1.00   15.00    --   92.50 -70.00 170.12   25
 32  \w    120.00 149.00   1.00   15.00    --   92.50  30.00 -90.00   29
 33  \w    131.00 156.00   1.00   15.00    --   92.50  61.00 -60.00   25
 34  \w     73.00 117.00   1.00   15.00    --   92.50  61.00 120.00   44
 35  \w     72.00  97.00   1.00   15.00    --   92.50 -70.00-158.27   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0575
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            17280
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.848
_diffrn_reflns_theta_max         66.848
_diffrn_reflns_theta_min         4.618
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35935
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (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    1.214
_exptl_crystal_description       plate
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.435
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0021(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         2844
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0730P)^2^+0.4447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1296
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2450
_reflns_number_total             2844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01049g2.cif
_cod_data_source_block           preex1_auto
_cod_depositor_comments          'Adding full bibliography for 7160696.cif.'
_cod_database_code               7160696
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.836
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C16(H16), C17(H17), C5(H5), C18(H18), C1(H1), C2(H2A), C3(H3), C4(H4)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
2.d Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              10108
_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 2.722
_oxdiff_exptl_absorpt_empirical_full_min 0.437