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_4035943
_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         'C14 H12 Cl N3 O2'
_chemical_formula_sum            'C14 H12 Cl N3 O2'
_chemical_formula_weight         289.72
_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'
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;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_audit_update_record
;
2018-05-29 deposited with the CCDC.
2018-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.8440(10)
_cell_angle_gamma                90
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_cell_length_c                   19.6202(3)
_cell_measurement_reflns_used    5216
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_cell_measurement_theta_min      4.0970
_cell_volume                     1264.11(4)
_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 0.995
_diffrn_measured_fraction_theta_max 0.990
_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    -49.00   7.00   0.50    0.20    --  -41.22  95.00-108.00  112
  2  \w    -24.00  65.00   0.50    0.20    --   41.22 -95.00 141.00  178
  3  \w     38.00 107.00   0.50    0.69    --  101.00 -95.00 141.00  138
  4  \w    108.00 135.00   0.50    0.69    --  101.00  95.00-108.00   54
  5  \w   -107.00 -75.00   0.50    0.20    --  -41.22 -21.00 120.00   64
  6  \w    -70.00 -40.00   0.50    0.20    --  -41.22 -21.00 120.00   60
  7  \w    -88.00 -28.00   0.50    0.20    --  -41.22 -43.00-180.00  120
  8  \w    -18.00  50.00   0.50    0.20    --   41.22 -32.00   0.00  136
  9  \w    -14.00  24.00   0.50    0.20    --   41.22-104.00-150.00   76
 10  \w     65.00 107.00   0.50    0.20    --   41.22  32.00   0.00   84
 11  \w     24.00  78.00   0.50    0.20    --   41.22  65.00 -30.00  108
 12  \w     61.00 103.00   0.50    0.20    --   41.22  54.00 -90.00   84
 13  \w     66.00 100.00   0.50    0.20    --   41.22  43.00-150.00   68
 14  \w     38.00  70.00   0.50    0.20    --   41.22-104.00-150.00   64
 15  \w     88.00 157.00   0.50    0.69    --  101.00  42.00-150.00  138
 16  \w    105.00 132.00   0.50    0.69    --  101.00  33.00   0.00   54
 17  \w     96.00 151.00   0.50    0.69    --  101.00  25.00-180.00  110
 18  \w     52.00  82.00   0.50    0.69    --  101.00 -68.00 150.00   60
 19  \w     37.00 115.00   0.50    0.69    --  101.00-111.00 -30.00  156
 20  \w     81.00 156.00   0.50    0.69    --  101.00  93.00-120.00  150
 21  \w     47.00  73.00   0.50    0.69    --  101.00 -25.00 120.00   52
 22  \w     64.00 108.00   0.50    0.69    --  101.00 -33.00  60.00   88
 23  \w     86.00 126.00   0.50    0.69    --  101.00 -77.00 150.00   80
 24  \w     38.00  70.00   0.50    0.69    --  101.00 -77.00 150.00   64
 25  \w     42.00  75.00   0.50    0.69    --  101.00 -59.00-180.00   66
 26  \w     78.00 103.00   0.50    0.69    --  101.00 -59.00-180.00   50
 27  \w     57.00 107.00   0.50    0.69    --  101.00 -33.00 -90.00  100
 28  \w     87.00 157.00   0.50    0.69    --  101.00  50.00-120.00  140
 29  \w    114.00 147.00   0.50    0.69    --  101.00 111.00-150.00   66
 30  \w    122.00 149.00   0.50    0.69    --  101.00   8.00  30.00   54
 31  \w     76.00 104.00   0.50    0.69    --  101.00   8.00  30.00   56
 32  \w     44.00  71.00   0.50    0.20    --   41.22 -95.00 141.00   54
 33  \w    -27.00   0.00   0.50    0.20    --  -41.22  32.00 -90.00   54
 34  \w    -12.00  18.00   0.50    0.20    --  -41.22  32.00-120.00   60
 35  \w    -54.00 -28.00   0.50    0.20    --  -41.22 -54.00 -30.00   52
 36  \w   -104.00 -77.00   0.50    0.20    --  -41.22 -54.00 -30.00   54
 37  \w    -18.00  14.00   0.50    0.20    --   41.22 -32.00-120.00   64
 38  \w     67.00  93.00   0.50    0.20    --   41.22  32.00 -60.00   52
 39  \w     20.00  46.00   0.50    0.20    --   41.22 -43.00 -60.00   52
 40  \w    -11.00  15.00   0.50    0.20    --   41.22 -43.00 -60.00   52
 41  \w     23.00  49.00   0.50    0.20    --   41.22 -43.00 120.00   52
 42  \w     39.00  65.00   0.50    0.69    --  101.00-111.00 -90.00   52
 43  \w     87.00 113.00   0.50    0.69    --  101.00 -87.00 -90.00   52
 44  \w     38.00  68.50   0.50    0.69    --  101.00 -87.00 -90.00   61
;
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'SuperNova, Single source at offset/far, HyPix3000'
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'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0043658000
_diffrn_orient_matrix_UB_12      0.1071517000
_diffrn_orient_matrix_UB_13      0.0354452000
_diffrn_orient_matrix_UB_21      0.2481952000
_diffrn_orient_matrix_UB_22      0.0331519000
_diffrn_orient_matrix_UB_23      -0.0330415000
_diffrn_orient_matrix_UB_31      -0.1800675000
_diffrn_orient_matrix_UB_32      0.0431924000
_diffrn_orient_matrix_UB_33      -0.0624370000
_diffrn_radiation_monochromator  mirror
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_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            8180
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.990
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_diffrn_reflns_theta_max         72.008
_diffrn_reflns_theta_min         4.129
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.732
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77446
_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 white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.522
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_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.733
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
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_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         2456
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0362
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_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0564P)^2^+0.8658P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.1006
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2335
_reflns_number_total             2456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02805_si_005.cif
_cod_data_source_block           reu127
_cod_database_code               4035943
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H12 Cl1 N3 O2'
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.93
_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:
 C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C12(H12), C5(H5), C2(H2A), C3(H3), C14(H14), C13(H13)
;
_shelx_res_checksum              10447
_shelx_hkl_checksum              85547
_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 1.326
_oxdiff_exptl_absorpt_empirical_full_min 0.763