The Cyclization/Rearrangement of α-Hydroxy Ketones with Trifluoromethyl N-acylhydrazones to Synthesize Multi-substituted Trifluoromethyloxazolines
Wang, Junjiao; Shang, Yongwei; Zhao, Xiujuan; Cui, Zhenli; Li, Yang; Wang, Ke-Hu; Huang, Danfeng; Hu, Yulai; Wang, Na; Feng, Lei; Chemical Communications  (2023) –; doi:10.1039/D3CC03854H

data_7132316
_publ_section_title
;
 The Cyclization/Rearrangement of \a-Hydroxy Ketones with Trifluoromethyl
 N-acylhydrazones to Synthesize Multi-substituted
 Trifluoromethyloxazolines
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03854H
_journal_year                    2023
_chemical_formula_moiety         'C18 H15 F3 N2 O2'
_chemical_formula_sum            'C18 H15 F3 N2 O2'
_chemical_formula_weight         696.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-04 deposited with the CCDC.	2023-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.3100(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   14.6254(2)
_cell_length_b                   14.0014(2)
_cell_length_c                   33.2503(4)
_cell_measurement_reflns_used    37802
_cell_measurement_temperature    300.51(10)
_cell_measurement_theta_max      77.2120
_cell_measurement_theta_min      2.7090
_cell_volume                     6753.53(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.51(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_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    -26.00  23.00   0.50    0.05    --   47.57 -19.00  90.00   98
  2  \w     45.00 110.00   0.50    0.05    --   47.57  48.00   9.00  130
  3  \w    145.00 170.00   0.50    0.14    --  107.75  48.00   9.00   50
  4  \w    107.00 175.00   0.50    0.14    --  107.75  37.00 -60.00  136
  5  \w    -17.00  19.00   0.50    0.05    --   47.57 -48.00-138.00   72
  6  \w    -27.00   8.00   0.50    0.05    --   47.57 -19.00  60.00   70
  7  \w     35.00  60.00   0.50    0.14    --  107.75 -57.00 -90.00   50
  8  \w     41.00 100.00   0.50    0.14    --  107.75 -77.00-180.00  118
  9  \w     36.00  61.00   0.50    0.14    --  107.75 -57.00   0.00   50
 10  \w     36.00  68.00   0.50    0.14    --  107.75 -77.00  30.00   64
 11  \w     35.00  62.00   0.50    0.14    --  107.75 -57.00  90.00   54
 12  \w     39.00  98.00   0.50    0.14    --  107.75 -77.00  60.00  118
 13  \w    -60.00 -28.00   0.50    0.14    -- -100.00  57.00-150.00   64
 14  \w    -69.00 -29.00   0.50    0.14    -- -100.00  57.00-180.00   80
 15  \w    -67.00 -31.00   0.50    0.14    -- -100.00  57.00 -60.00   72
 16  \w    -61.00 -30.00   0.50    0.14    -- -100.00  57.00 -30.00   62
 17  \w    -56.00 -30.00   0.50    0.14    -- -100.00  57.00  30.00   52
 18  \w    -57.00 -29.00   0.50    0.14    -- -100.00  48.00   9.00   56
 19  \w    -60.00 -27.00   0.50    0.14    -- -100.00  57.00 120.00   66
 20  \w    -57.00 -29.00   0.50    0.05    --  -47.57  48.00   9.00   56
 21  \w   -170.00 -99.00   0.50    0.14    -- -100.00 -37.00 120.00  142
 22  \w   -163.00-137.00   0.50    0.14    -- -100.00 -99.00   0.00   52
 23  \w   -125.00 -97.00   0.50    0.14    -- -100.00 -99.00   0.00   56
 24  \w   -116.00 -38.00   0.50    0.05    --  -47.57 -48.00-138.00  156
 25  \w   -168.00 -87.00   0.50    0.14    -- -100.00 -48.00-138.00  162
 26  \w   -119.00 -93.00   0.50    0.05    --  -47.57 -48.00-138.00   52
 27  \w     -8.00  19.00   0.50    0.05    --  -47.57  19.00   0.00   54
 28  \w    -48.00 -23.00   0.50    0.05    --  -47.57 125.00 120.00   50
 29  \w    -95.00 -34.00   0.50    0.05    --  -47.57 -57.00 120.00  122
 30  \w   -121.00 -85.00   0.50    0.05    --  -47.57 -37.00  30.00   72
 31  \w    -93.00 -66.00   0.50    0.05    --  -47.57 125.00 120.00   54
 32  \w    -78.00 -36.00   0.50    0.05    --  -47.57 -37.00  30.00   84
 33  \w    -25.00  23.00   0.50    0.05    --   47.57 -19.00 -30.00   96
 34  \w     49.00  75.00   0.50    0.05    --   47.57  57.00 120.00   52
 35  \w   -171.00 -87.00   0.50    0.14    -- -100.00 -47.00 147.17  168
 36  \w   -134.00 -83.00   0.50    0.14    -- -100.00 -77.00  90.00  102
 37  \w   -169.00-135.00   0.50    0.14    -- -100.00 -19.00 -60.00   68
 38  \w   -172.00-141.00   0.50    0.14    -- -100.00 -57.00   0.00   62
 39  \w   -131.00 -86.00   0.50    0.14    -- -100.00 -57.00   0.00   90
 40  \w   -126.00 -99.00   0.50    0.14    -- -100.00 -19.00 -60.00   54
 41  \w   -112.00 -86.00   0.50    0.14    -- -100.00 -50.00 136.93   52
 42  \w   -167.00-141.00   0.50    0.14    -- -100.00 -77.00  90.00   52
 43  \w   -110.00 -84.00   0.50    0.14    -- -100.00 -61.00 115.03   52
 44  \w   -109.00 -83.00   0.50    0.14    -- -100.00 -63.00 130.75   52
 45  \w    -69.00 -44.00   0.50    0.14    -- -100.00  57.00   0.00   50
 46  \w   -108.00 -82.00   0.50    0.14    -- -100.00 -65.00 114.30   52
 47  \w   -152.00-127.00   0.50    0.14    -- -100.00 -19.00 150.00   50
 48  \w   -163.00 -85.00   0.50    0.14    -- -100.00 -57.00  83.62  156
 49  \w   -136.00-110.00   0.50    0.14    -- -100.00-125.00 -30.00   52
 50  \w   -117.00 -88.00   0.50    0.14    -- -100.00 -37.00 150.00   58
 51  \w   -108.00 -83.00   0.50    0.14    -- -100.00 -63.00 143.42   50
 52  \w   -164.00-138.00   0.50    0.14    -- -100.00 -75.00 137.89   52
 53  \w   -150.00-124.00   0.50    0.14    -- -100.00 -59.00 110.36   52
 54  \w   -110.00 -84.00   0.50    0.14    -- -100.00 -59.00 110.36   52
 55  \w   -112.00 -82.00   0.50    0.14    -- -100.00 -65.00 101.66   60
 56  \w   -151.00-125.00   0.50    0.14    -- -100.00 -72.00 161.87   52
 57  \w   -102.00 -77.00   0.50    0.14    -- -100.00 -77.00 148.76   50
 58  \w   -110.00 -85.00   0.50    0.14    -- -100.00 -55.00 128.23   50
 59  \w    -79.00 -30.00   0.50    0.14    -- -100.00 125.00-150.00   98
 60  \w   -104.00 -79.00   0.50    0.14    -- -100.00 -72.00 161.87   50
 61  \w   -105.00 -80.00   0.50    0.14    -- -100.00 -70.00 115.65   50
 62  \w   -166.00-102.00   0.50    0.14    -- -100.00 -57.00  60.00  128
 63  \w   -103.00 -78.00   0.50    0.14    -- -100.00 -75.00 137.89   50
 64  \w     37.00 103.00   0.50    0.14    --  107.75 -99.00 -90.00  132
 65  \w     96.00 132.00   0.50    0.14    --  107.75  57.00 150.00   72
 66  \w     76.00 102.00   0.50    0.14    --  107.75 -77.00  60.00   52
 67  \w    121.00 174.00   0.50    0.14    --  107.75 125.00 -30.00  106
 68  \w     76.00 102.00   0.50    0.14    --  107.75 125.00 -30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0930423000
_diffrn_orient_matrix_UB_12      0.0295785000
_diffrn_orient_matrix_UB_13      0.0133632000
_diffrn_orient_matrix_UB_21      -0.0510815000
_diffrn_orient_matrix_UB_22      -0.0591240000
_diffrn_orient_matrix_UB_23      -0.0349103000
_diffrn_orient_matrix_UB_31      0.0031581000
_diffrn_orient_matrix_UB_32      -0.0879557000
_diffrn_orient_matrix_UB_33      0.0280142000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            57519
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.467
_diffrn_reflns_theta_min         2.680
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.966
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.370
_exptl_crystal_description       block
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 4827 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.32(6)
_refine_ls_extinction_coef       0.00024(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     906
_refine_ls_number_reflns         12797
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0467
_refine_ls_R_factor_gt           0.0437
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0700P)^2^+2.0660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1181
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    0.893
_reflns_Friedel_fraction_max     0.818
_reflns_number_gt                11817
_reflns_number_total             12797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03854h2.cif
_cod_data_source_block           shangyw_1011_auto
_cod_depositor_comments
;

2024-12-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C72 H60 F12 N8 O8'
_cod_original_formula_weight         1393.28
_cod_original_formula_moiety         '4(C18 H15 F3 N2 O2)'
_cod_original_formula_units_Z            4
_cod_original_cell_volume        6753.52(16)
_cod_database_code               7132316
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.877
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C21(H21), C39(H39), C57(H57)
2.b Aromatic/amide H refined with riding coordinates:
 N4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), N2(H2), C23(H23), C24(H24), C25(H25), C26(H26),
 C27(H27), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), N6(H6A), C41(H41),
 C42(H42), C43(H43), C44(H44), C45(H45), C49(H49), C50(H50), C51(H51), C52(H52),
  C53(H53), N8(H8A), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C68(H68),
  C69(H69), C70(H70), C71(H71), C72(H72)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C28(H28A,H28B,H28C), C46(H46A,H46B,H46C), C64(H64A,H64B,
 H64C)
;
_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 4.832
_oxdiff_exptl_absorpt_empirical_full_min 0.485