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_4035944
_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 H14 N4 O2'
_chemical_formula_sum            'C14 H14 N4 O2'
_chemical_formula_weight         270.29
_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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_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-28
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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
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_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
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_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
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_diffrn_measured_fraction_theta_max 0.987
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;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -104.00 -78.00   0.50    0.24    --  -41.35 148.00   1.00   52
  2  \w    -71.00 -28.00   0.50    0.24    --  -41.35 148.00   1.00   86
  3  \w     19.00  45.00   0.50    0.24    --   41.35-148.00 -46.00   52
  4  \w     86.00 119.00   0.50    0.96    --  101.00-123.00 117.00   66
  5  \w     90.00 130.00   0.50    0.96    --  101.00-148.00 -46.00   80
  6  \w    104.00 130.00   0.50    0.96    --  101.00 123.00-162.00   52
  7  \w     40.00  65.00   0.50    0.96    --  101.00-123.00 117.00   50
  8  \w     92.00 130.00   0.50    0.96    --  101.00 148.00   1.00   76
  9  \w    -71.00 -34.00   0.50    0.24    --  -41.35 -21.00  30.00   74
 10  \w   -101.00 -75.00   0.50    0.24    --  -41.35 -21.00  30.00   52
 11  \w    -65.00 -27.00   0.50    0.24    --  -41.35 123.00-162.00   76
 12  \w    -23.00  50.00   0.50    0.24    --   41.35 -32.00 -90.00  146
 13  \w     14.00  64.00   0.50    0.24    --   41.35-104.00-180.00  100
 14  \w     41.00  66.00   0.50    0.24    --   41.35-123.00 117.00   50
 15  \w     75.00 101.00   0.50    0.24    --   41.35  32.00   0.00   52
 16  \w     61.00 105.00   0.50    0.24    --   41.35  77.00   0.00   88
 17  \w     20.00  47.00   0.50    0.24    --   41.35  77.00   0.00   54
 18  \w     67.00  97.00   0.50    0.24    --   41.35  32.00-120.00   60
 19  \w    122.00 148.00   0.50    0.96    --  101.00  33.00  30.00   52
 20  \w     70.00 115.00   0.50    0.96    --  101.00-111.00 -60.00   90
 21  \w     35.00 110.00   0.50    0.96    --  101.00 -25.00-150.00  150
 22  \w     37.00 123.00   0.50    0.96    --  101.00 -68.00  90.00  172
 23  \w     40.00 117.00   0.50    0.96    --  101.00 -50.00-120.00  154
 24  \w     85.00 152.00   0.50    0.96    --  101.00  50.00  30.00  134
 25  \w     89.00 118.00   0.50    0.96    --  101.00  42.00 150.00   58
 26  \w    102.00 156.00   0.50    0.96    --  101.00  33.00   0.00  108
 27  \w     83.00 117.00   0.50    0.96    --  101.00  59.00  60.00   68
 28  \w    121.00 147.00   0.50    0.96    --  101.00  42.00 150.00   52
 29  \w     76.00 109.00   0.50    0.96    --  101.00 -25.00  30.00   66
 30  \w     60.00 125.00   0.50    0.96    --  101.00 -77.00 -30.00  130
 31  \w     38.00  66.00   0.50    0.96    --  101.00 -25.00  30.00   56
 32  \w    105.00 141.00   0.50    0.96    --  101.00 111.00-120.00   72
 33  \w     17.00  46.00   0.50    0.24    --   41.35  77.00 -30.00   58
 34  \w    -47.00 -15.00   0.50    0.24    --  -41.35  32.00  90.00   64
 35  \w   -100.00 -70.00   0.50    0.24    --  -41.35 -54.00 -90.00   60
 36  \w    -59.00 -33.00   0.50    0.24    --  -41.35 -54.00 -90.00   52
 37  \w     18.00  23.50   0.50    0.24    --   41.35  77.00-180.00   11
;
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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_22      -0.0215627000
_diffrn_orient_matrix_UB_23      -0.1566072000
_diffrn_orient_matrix_UB_31      -0.3084618000
_diffrn_orient_matrix_UB_32      0.0049336000
_diffrn_orient_matrix_UB_33      -0.0195372000
_diffrn_radiation_monochromator  mirror
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_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0371
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            6870
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.987
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_diffrn_reflns_theta_max         71.808
_diffrn_reflns_theta_min         3.284
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86381
_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.
;
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_exptl_crystal_density_diffrn    1.450
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_exptl_crystal_F_000             568
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_exptl_crystal_size_mid          0.6
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_refine_diff_density_max         0.705
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_refine_diff_density_rms         0.058
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_refine_ls_hydrogen_treatment    constr
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_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0626P)^2^+0.7561P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2184
_reflns_number_total             2395
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02805_si_004.cif
_cod_data_source_block           reu126
_cod_database_code               4035944
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H14 N4 O2'
_reflns_odcompleteness_completeness 99.68
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C3(H3), C4(H4), C13(H13), C5(H5), C12(H12)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              98635
_shelx_hkl_checksum              74966
_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 1.900
_oxdiff_exptl_absorpt_empirical_full_min 0.529