Rethinking Hydrolytic Imidazoline Ring Expansion: A Common Approach to the Preparation of Medium-Sized Rings via Side-Chain Insertion into [1.4]Oxa- and [1.4]Thiazepinone Scaffolds.
Reutskaya, Elena; Osipyan, Angelina; Sapegin, Alexander; Novikov, Alexander S.; Krasavin, Mikhail; The Journal of organic chemistry 84 (2019) 1693–1705; doi:10.1021/acs.joc.8b02805

data_4035941
_publ_section_title
;
 Rethinking Hydrolytic Imidazoline Ring Expansion: A Common Approach to
 the Preparation of Medium-Sized Rings via Side-Chain Insertion into
 [1.4]Oxa- and [1.4]Thiazepinone Scaffolds.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1693
_journal_page_last               1705
_journal_paper_doi               10.1021/acs.joc.8b02805
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C15 H12 F3 N3 O2'
_chemical_formula_sum            'C15 H12 F3 N3 O2'
_chemical_formula_weight         323.28
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_audit_update_record
;
2018-05-27 deposited with the CCDC.
2018-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                104.090(15)
_cell_angle_beta                 92.295(14)
_cell_angle_gamma                103.600(16)
_cell_formula_units_Z            2
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_cell_length_b                   10.587(2)
_cell_length_c                   13.334(2)
_cell_measurement_reflns_used    1345
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_cell_measurement_theta_max      70.5510
_cell_measurement_theta_min      3.3380
_cell_volume                     680.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.963
_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  13.00   0.50    0.81    --  -41.35  89.00  53.00  104
  2  \w     96.00 147.00   0.50    3.10    --  101.00  89.00  53.00  102
  3  \w     79.00 129.00   0.50    3.10    --  101.00 -89.00 -62.00  100
  4  \w     36.00  62.00   0.50    3.10    --  101.00 -89.00 -62.00   52
  5  \w    -15.00  19.00   0.50    0.81    --  -41.35  32.00-150.00   68
  6  \w    -50.00 -24.00   0.50    0.81    --  -41.35 -54.00 -60.00   52
  7  \w    -60.00 -30.00   0.50    0.81    --  -41.35 -43.00  60.00   60
  8  \w    -48.00 -20.00   0.50    0.81    --  -41.35  32.00-150.00   56
  9  \w    -97.00 -71.00   0.50    0.81    --  -41.35 -43.00  60.00   52
 10  \w   -104.00 -63.00   0.50    0.81    --  -41.35 -54.00 -60.00   82
 11  \w    -44.00 -13.00   0.50    0.81    --  -41.35 138.00 150.00   62
 12  \w    -96.00 -59.00   0.50    0.81    --  -41.35 138.00 150.00   74
 13  \w     34.00  65.00   0.50    0.81    --   41.35  21.00 150.00   62
 14  \w     74.00 107.00   0.50    0.81    --   41.35  21.00 150.00   66
 15  \w     23.00  49.00   0.50    0.81    --   41.35 -32.00 120.00   52
 16  \w     25.00  61.00   0.50    0.81    --   41.35  54.00  30.00   72
 17  \w     37.00  64.00   0.50    0.81    --   41.35-104.00-180.00   54
 18  \w    -13.00  12.00   0.50    0.81    --   41.35 -65.00   0.00   50
 19  \w    -11.00  17.00   0.50    0.81    --   41.35 -32.00 120.00   56
 20  \w     -4.00  39.00   0.50    0.81    --   41.35 -89.00 -62.00   86
 21  \w      9.00  34.00   0.50    0.81    --   41.35-104.00-180.00   50
 22  \w     26.00  61.00   0.50    0.81    --   41.35 -65.00   0.00   70
 23  \w     43.00  68.00   0.50    0.81    --   41.35 -89.00 -62.00   50
 24  \w     30.00  64.00   0.50    0.81    --   41.35  43.00 -90.00   68
 25  \w     66.00  97.00   0.50    0.81    --   41.35  54.00  30.00   62
 26  \w     87.00 155.00   0.50    3.10    --  101.00  50.00 -60.00  136
 27  \w     83.00 117.00   0.50    3.10    --  101.00  93.00  90.00   68
 28  \w     74.00 114.00   0.50    3.10    --  101.00-111.00-120.00   80
 29  \w     50.00 116.00   0.50    3.10    --  101.00 -59.00 120.00  132
 30  \w     89.00 114.00   0.50    3.10    --  101.00 -59.00  30.00   50
 31  \w    121.00 156.00   0.50    3.10    --  101.00  25.00 -90.00   70
 32  \w    104.00 153.00   0.50    3.10    --  101.00  42.00-150.00   98
 33  \w     84.00 109.00   0.50    3.10    --  101.00 -33.00 120.00   50
 34  \w    115.00 141.00   0.50    3.10    --  101.00  50.00 150.00   52
 35  \w     38.00 122.00   0.50    3.10    --  101.00 -68.00-120.00  168
 36  \w     95.00 120.00   0.50    3.10    --  101.00 -59.00 -30.00   50
 37  \w     59.00  85.00   0.50    3.10    --  101.00 -59.00 -30.00   52
 38  \w     80.00 150.00   0.50    3.10    --  101.00 111.00  90.00  140
 39  \w     94.00 145.00   0.50    3.10    --  101.00  42.00  60.00  102
 40  \w     45.00  96.00   0.50    3.10    --  101.00-133.00 -60.00  102
 41  \w     41.00  68.00   0.50    3.10    --  101.00 -33.00 120.00   54
 42  \w     97.00 137.00   0.50    3.10    --  101.00  25.00 120.00   80
 43  \w     67.00 125.00   0.50    3.10    --  101.00 -93.00   0.00  116
 44  \w     39.00  87.00   0.50    3.10    --  101.00 -50.00  30.00   96
 45  \w     38.00 122.00   0.50    3.10    --  101.00-133.00-150.00  168
 46  \w     76.00 124.00   0.50    3.10    --  101.00-133.00   0.00   96
 47  \w    127.00 157.00   0.50    3.10    --  101.00  50.00 -30.00   60
 48  \w     93.00 150.00   0.50    3.10    --  101.00  33.00   0.00  114
 49  \w     98.00 134.00   0.50    3.10    --  101.00  33.00  30.00   72
 50  \w     94.00 120.00   0.50    3.10    --  101.00  25.00 -90.00   52
 51  \w     68.00 100.00   0.50    3.10    --  101.00 -87.00  60.00   64
 52  \w     70.00 115.00   0.50    3.10    --  101.00-111.00-150.00   90
 53  \w     85.00 111.00   0.50    3.10    --  101.00  50.00 -30.00   52
 54  \w     85.00 110.00   0.50    3.10    --  101.00  59.00-150.00   50
 55  \w     39.00 114.00   0.50    3.10    --  101.00 -42.00 -60.00  150
 56  \w     33.00  94.00   0.50    3.10    --  101.00 -93.00 120.00  122
 57  \w     17.00  43.00   0.50    0.81    --   41.35  77.00-180.00   52
 58  \w    -46.00 -17.00   0.50    0.81    --    0.00 125.00 176.52   58
 59  \w    -13.00  12.00   0.50    0.81    --   24.00 106.00  78.75   50
 60  \w    -40.00 -15.00   0.50    0.81    --   24.00 150.00 -88.59   50
 61  \w     -1.00  24.00   0.50    0.81    --   28.00  95.00  93.55   50
 62  \w     -3.00  22.00   0.50    0.81    --   28.00  96.00-155.20   50
 63  \w      4.00  29.00   0.50    0.81    --   32.00  88.00 -25.88   50
 64  \w      5.00  30.00   0.50    0.81    --   32.00  85.00 -61.30   50
 65  \w      3.00  28.00   0.50    0.81    --   32.00  90.00-146.69   50
 66  \w      9.00  34.00   0.50    0.81    --   36.00  84.00  95.17   50
 67  \w      9.00  34.00   0.50    0.81    --   36.00  84.00  19.41   50
 68  \w      9.00  34.00   0.50    0.81    --   36.00  84.00 -84.45   50
 69  \w     15.00  40.00   0.50    0.81    --   40.00  80.00-143.85   50
 70  \w     30.00  55.00   0.50    0.81    --   41.35 -43.00 -60.00   50
 71  \w    -13.00  22.00   0.50    0.81    --   41.35 -43.00 -60.00   70
 72  \w     21.00  47.00   0.50    0.81    --   41.35  77.00 150.00   52
 73  \w     19.00  44.00   0.50    0.81    --   44.00  80.00-121.73   50
 74  \w     19.00  44.00   0.50    0.81    --   44.00  78.00  94.70   50
 75  \w     19.00  44.00   0.50    0.81    --   44.00  82.00 -48.54   50
 76  \w     30.00  56.00   0.50    0.81    --   52.00  72.00  82.16   52
 77  \w     81.00 107.00   0.50    0.81    --   52.00  77.00 -94.43   52
 78  \w     27.00  53.00   0.50    0.81    --   52.00  77.00 153.99   52
 79  \w     33.00  58.00   0.50    0.81    --   52.00  75.00 -24.56   50
 80  \w     79.00 106.00   0.50    0.81    --   52.00  72.00  82.16   54
 81  \w     39.00  75.00   0.50    0.81    --   52.00  77.00 -94.43   72
 82  \w     34.00  44.50   0.50    0.81    --   56.00  77.00-125.13   21
;
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'SuperNova, Single source at offset/far, HyPix3000'
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'CrysAlisPro convention (1999,Acta A55,543-557)'
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_diffrn_orient_matrix_UB_21      0.1842321000
_diffrn_orient_matrix_UB_22      -0.0935740000
_diffrn_orient_matrix_UB_23      0.0079972000
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_diffrn_orient_matrix_UB_32      -0.0854890000
_diffrn_orient_matrix_UB_33      0.0486932000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0672
_diffrn_reflns_av_unetI/netI     0.0671
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
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_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6927
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_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.413
_diffrn_reflns_theta_min         3.436
_diffrn_source                   'micro-focus sealed X-ray tube'
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_exptl_absorpt_coefficient_mu    1.170
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63337
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
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    1.578
_exptl_crystal_description       prism
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.584
_refine_diff_density_min         -0.521
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         2609
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_refine_ls_R_factor_all          0.0888
_refine_ls_R_factor_gt           0.0674
_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^)+(0.1319P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1774
_refine_ls_wR_factor_ref         0.1961
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1897
_reflns_number_total             2609
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02805_si_003.cif
_cod_data_source_block           reu-093
_cod_original_cell_volume        680.2(2)
_cod_database_code               4035941
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 H12 F3 N3 O2'
_reflns_odcompleteness_completeness 97.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C5(H5), C14(H14), C12(H12), C3(H3), C2(H2A), C4(H4)
;
_shelx_res_checksum              11648
_shelx_hkl_checksum              70549
_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 4.098
_oxdiff_exptl_absorpt_empirical_full_min 0.389