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_4035945
_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_absolute_configuration unk
_chemical_formula_moiety         'C17 H15 N3 O2'
_chemical_formula_sum            'C17 H15 N3 O2'
_chemical_formula_weight         293.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-28
_audit_creation_method
;
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                 90
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_cell_length_c                   13.7464(6)
_cell_measurement_reflns_used    5920
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_cell_measurement_theta_min      4.9790
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_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)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(10)
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_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -93.00 -65.00   0.50    0.20    --  -41.22 164.00 -82.00   56
  2  \w    -47.00 -21.00   0.50    0.20    --  -41.22 109.00  40.00   52
  3  \w    -24.00  28.00   0.50    0.20    --  -41.22  20.00 -67.00  104
  4  \w    -61.00 -35.00   0.50    0.20    --  -41.22 164.00 -82.00   52
  5  \w    -94.00 -56.00   0.50    0.20    --  -41.22 -20.00 125.00   76
  6  \w     53.00  78.00   0.50    0.20    --   41.22 164.00 -82.00   50
  7  \w     21.00  46.00   0.50    0.20    --   41.22-109.00 -55.00   50
  8  \w     50.00  76.00   0.50    0.20    --   41.22  20.00 -67.00   52
  9  \w     91.00 128.00   0.50    0.25    --  101.00 109.00  40.00   74
 10  \w    112.00 137.00   0.50    0.25    --  101.00  20.00 -67.00   50
 11  \w     33.00 108.00   0.50    0.25    --  101.00 -20.00 125.00  150
 12  \w    101.00 127.00   0.50    0.25    --  101.00 116.00 129.00   52
 13  \w     78.00 103.00   0.50    0.25    --  101.00 164.00 -82.00   50
 14  \w     75.00 113.00   0.50    0.25    --  101.00-116.00  40.00   76
 15  \w     82.00 113.00   0.50    0.25    --  101.00-109.00 -55.00   62
 16  \w    -11.00  17.00   0.50    0.20    --  -41.22 104.00 -90.00   56
 17  \w    -76.00 -19.00   0.50    0.20    --  -41.22 104.00 -90.00  114
 18  \w     37.00  63.00   0.50    0.20    --   41.22  32.00  30.00   52
 19  \w    -12.00  53.00   0.50    0.20    --   41.22 -43.00  90.00  130
 20  \w     -1.00  24.00   0.50    0.20    --   41.22 -20.00 125.00   50
 21  \w     51.00 114.00   0.50    0.25    --  101.00-111.00-180.00  126
 22  \w     54.00 114.00   0.50    0.25    --  101.00 -42.00 -30.00  120
 23  \w     84.00 110.00   0.50    0.25    --  101.00-111.00 -90.00   52
 24  \w     36.00  74.00   0.50    0.25    --  101.00-111.00 -90.00   76
 25  \w    108.00 152.00   0.50    0.25    --  101.00  33.00 -30.00   88
 26  \w     37.00  89.00   0.50    0.25    --  101.00 -33.00-120.00  104
 27  \w     88.00 113.00   0.50    0.20    --   41.22-164.00-107.00   50
 28  \w     12.00  39.00   0.50    0.20    --   41.22 -32.00 150.00   54
 29  \w     41.00  97.00   0.50    0.25    --  101.00-111.00 120.00  112
 30  \w     33.00  59.00   0.50    0.25    --  101.00 -17.00 -90.00   52
 31  \w     69.00 106.00   0.50    0.25    --  101.00 -17.00 -90.00   74
 32  \w     82.00 108.00   0.50    0.25    --  101.00  93.00-150.00   52
 33  \w    114.00 140.00   0.50    0.25    --  101.00  93.00-150.00   52
 34  \w     84.00 110.00   0.50    0.25    --  101.00  59.00-150.00   52
 35  \w     49.00  75.00   0.50    0.25    --  101.00 -77.00 120.00   52
 36  \w     86.00 124.00   0.50    0.25    --  101.00 -77.00 120.00   76
 37  \w    132.00 157.00   0.50    0.25    --  101.00  33.00 -90.00   50
 38  \w     47.00  83.00   0.50    0.25    --  101.00 -77.00  90.00   72
;
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'SuperNova, Single source at offset/far, HyPix3000'
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_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0396042000
_diffrn_orient_matrix_UB_12      -0.1309567000
_diffrn_orient_matrix_UB_13      -0.0094406000
_diffrn_orient_matrix_UB_21      0.0213955000
_diffrn_orient_matrix_UB_22      0.0157946000
_diffrn_orient_matrix_UB_23      -0.1103059000
_diffrn_orient_matrix_UB_31      0.1614965000
_diffrn_orient_matrix_UB_32      0.0299865000
_diffrn_orient_matrix_UB_33      0.0169671000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7780
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.958
_diffrn_reflns_theta_min         5.042
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.741
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47666
_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    1.353
_exptl_crystal_description       prism
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1118 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         2797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0635P)^2^+0.4370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                2720
_reflns_number_total             2797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02805_si_007.cif
_cod_data_source_block           reu131
_cod_database_code               4035945
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H15 N3 O2'
_reflns_odcompleteness_completeness 100.00
_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), C10(H10A,H10B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), N1(H1), C5(H5), C14(H14), C15(H15), C13(H13), C4(H4), C2(H2A), C3(H3)
;
_shelx_res_checksum              32975
_shelx_hkl_checksum              25081
_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 1.746
_oxdiff_exptl_absorpt_empirical_full_min 0.449