Electrophilic aromatic substitution using fluorinated isoxazolines at the C5 position via C–F bond cleavage
Sato, Kazuyuki; Kuroki, Tomohiro; Minami, Haruka; Sato, Azusa; Karuo, Yukiko; Tarui, Atsushi; Kawai, Kentaro; Omote, Masaaki; RSC Advances 14 (2024) 39543–39549; doi:10.1039/D4RA07102F

data_7249698
_publ_section_title
;
 Electrophilic aromatic substitution using fluorinated isoxazolines at the
 C5 position via C--F bond cleavage
;
_journal_issue                   53
_journal_name_full               'RSC Advances'
_journal_page_first              39543
_journal_page_last               39549
_journal_paper_doi               10.1039/D4RA07102F
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C20 H16 F2 N2 O'
_chemical_formula_sum            'C20 H16 F2 N2 O'
_chemical_formula_weight         338.35
_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             2024-04-10
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-04-19 deposited with the CCDC.	2024-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                96.3100(10)
_cell_angle_beta                 97.1640(10)
_cell_angle_gamma                93.9910(10)
_cell_formula_units_Z            4
_cell_length_a                   8.14050(10)
_cell_length_b                   12.07940(10)
_cell_length_c                   17.1421(3)
_cell_measurement_reflns_used    31356
_cell_measurement_temperature    120.0(5)
_cell_measurement_theta_max      77.1460
_cell_measurement_theta_min      2.6630
_cell_volume                     1656.39(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -74.00  31.00   0.50    0.17    --  -43.07  82.00  79.00  210
  2  \w    -30.00  74.00   0.50    0.17    --   43.07 -82.00 -42.00  208
  3  \w   -136.00 -30.00   0.50    0.67    -- -104.50  82.00  79.00  212
  4  \w   -174.00 -79.00   0.50    0.67    -- -104.50 -82.00 -42.00  190
  5  \w     39.00 144.00   0.50    0.67    --  113.00 -82.00 -42.00  210
  6  \w     86.00 178.00   0.50    0.67    --  113.00  82.00  79.00  184
  7  \w    -25.00  38.00   0.50    0.17    --  -43.07  19.00-120.00  126
  8  \w    -25.00  38.00   0.50    0.17    --  -43.07  19.00 120.00  126
  9  \w    -25.00  38.00   0.50    0.17    --  -43.07  19.00   0.00  126
 10  \w     12.00 124.00   0.50    0.17    --   43.07  19.00   0.00  224
 11  \w    -30.00  65.00   0.50    0.17    --   43.07 -57.00-180.00  190
 12  \w     19.00  95.00   0.50    0.17    --   43.07-125.00 120.00  152
 13  \w   -123.00 -30.00   0.50    0.67    -- -104.50 140.00 -56.36  186
 14  \w     40.00 107.00   0.50    0.67    --  113.00-109.00 145.85  134
 15  \w     41.00 112.00   0.50    0.67    --  113.00-125.00 -90.00  142
 16  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00 -30.00  134
 17  \w     40.00 108.00   0.50    0.67    --  113.00-108.00 -62.39  136
 18  \w     84.00 178.00   0.50    0.67    --  113.00  77.00-180.00  188
 19  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00  90.00  136
 20  \w     90.00 178.00   0.50    0.67    --  113.00  61.00-150.00  176
 21  \w     91.00 178.00   0.50    0.67    --  113.00  45.00 -60.00  174
 22  \w     89.00 178.00   0.50    0.67    --  113.00  30.00-120.00  178
 23  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00   0.00   74
 24  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00 -30.00   74
 25  \w     90.00 178.00   0.50    0.67    --  113.00  61.00-120.00  176
 26  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00  90.00  134
 27  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00 120.00   74
 28  \w     41.00 112.00   0.50    0.67    --  113.00-125.00 -60.00  142
 29  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00  60.00  136
 30  \w     89.00 178.00   0.50    0.67    --  113.00  30.00  60.00  178
 31  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00 -90.00  134
 32  \w     41.00 110.00   0.50    0.67    --  113.00-123.00-101.27  138
 33  \w     89.00 178.00   0.50    0.67    --  113.00  30.00-180.00  178
 34  \w     90.00 178.00   0.50    0.67    --  113.00  61.00 120.00  176
 35  \w     90.00 178.00   0.50    0.67    --  113.00  57.00 -40.19  176
 36  \w     90.00 178.00   0.50    0.67    --  113.00  61.00 -90.00  176
 37  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00  30.00   74
 38  \w     41.00 112.00   0.50    0.67    --  113.00-125.00 150.00  142
 39  \w     80.00 178.00   0.50    0.67    --  113.00 125.00 -60.00  196
 40  \w     40.00 106.00   0.50    0.67    --  113.00 -93.00 137.99  132
 41  \w     41.00 117.00   0.50    0.67    --  113.00-133.00  76.88  152
 42  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00-120.00  134
 43  \w     91.00 178.00   0.50    0.67    --  113.00  45.00  60.00  174
 44  \w     80.00 178.00   0.50    0.67    --  113.00 125.00  60.00  196
 45  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00-180.00  134
 46  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00 -60.00  136
 47  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00 120.00  136
 48  \w     91.00 178.00   0.50    0.67    --  113.00  45.00  30.00  174
 49  \w     89.00 178.00   0.50    0.67    --  113.00  30.00   0.00  178
 50  \w     41.00 112.00   0.50    0.67    --  113.00-125.00  90.00  142
 51  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00-180.00   74
 52  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00  60.00   74
 53  \w     39.00  76.00   0.50    0.67    --  113.00 -61.00 150.00   74
 54  \w     39.00 121.00   0.50    0.67    --  113.00-138.00-130.24  164
 55  \w     89.00 178.00   0.50    0.67    --  113.00  30.00 120.00  178
 56  \w     39.00 106.00   0.50    0.67    --  113.00 -77.00 150.00  134
 57  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00 -30.00  136
 58  \w     38.00 106.00   0.50    0.67    --  113.00 -95.00   0.00  136
 59  \w     41.00 112.00   0.50    0.67    --  113.00-125.00 -30.00  142
 60  \w     41.00 112.00   0.50    0.67    --  113.00-125.00  60.00  142
 61  \w     41.00 112.00   0.50    0.67    --  113.00-125.00 120.00  142
 62  \w     39.00 113.00   0.50    0.67    --  113.00 -79.00 171.54  148
 63  \w     39.00 130.00   0.50    0.67    --  113.00-151.00  40.72  182
 64  \w     84.00 178.00   0.50    0.67    --  113.00  77.00  60.00  188
 65  \w     90.00 178.00   0.50    0.67    --  113.00  61.00 150.00  176
 66  \w     14.00 117.00   0.50    0.17    --   43.07  77.00-180.00  206
 67  \w     14.00 117.00   0.50    0.17    --   43.07  77.00   0.00  206
 68  \w     14.00 117.00   0.50    0.17    --   43.07  77.00 -60.00  206
 69  \w     21.00 117.00   0.50    0.17    --   43.07  57.00 150.00  192
 70  \w     21.00 117.00   0.50    0.17    --   43.07  57.00  60.00  192
 71  \w      9.00  42.00   0.50    0.17    --   43.07  89.00  67.39   66
 72  \w     21.00 120.00   0.50    0.17    --   43.07  38.00 150.00  198
 73  \w     14.00 117.00   0.50    0.17    --   43.07  77.00-120.00  206
 74  \w     21.00 120.00   0.50    0.17    --   43.07  38.00  30.00  198
 75  \w     14.00 117.00   0.50    0.17    --   43.07  77.00  60.00  206
 76  \w     21.00 117.00   0.50    0.17    --   43.07  57.00-150.00  192
 77  \w     21.00 117.00   0.50    0.17    --   43.07  57.00 -90.00  192
 78  \w   -174.00 -75.00   0.50    0.67    -- -104.50 -77.00  41.84  198
 79  \w   -174.00 -76.00   0.50    0.67    -- -104.50 -75.00-177.09  196
 80  \w   -174.00 -75.00   0.50    0.67    -- -104.50 -77.00   0.00  198
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0842134000
_diffrn_orient_matrix_UB_12      0.0036962000
_diffrn_orient_matrix_UB_13      -0.0754287000
_diffrn_orient_matrix_UB_21      -0.1073035000
_diffrn_orient_matrix_UB_22      0.0938097000
_diffrn_orient_matrix_UB_23      -0.0244314000
_diffrn_orient_matrix_UB_31      0.1342961000
_diffrn_orient_matrix_UB_32      0.0881407000
_diffrn_orient_matrix_UB_33      0.0451366000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0133
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            13056
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.956
_diffrn_reflns_theta_min         2.617
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.834
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80863
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethylacetate'
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     546
_refine_ls_number_reflns         13056
_refine_ls_number_restraints     169
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0547
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0732P)^2^+0.6159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1394
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11518
_reflns_number_total             13056
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9757\% 
around [0.00 0.00 1.00] (reciprocal) or [0.27 0.16 0.95] (direct)
;
_cod_data_source_file            d4ra07102f2.cif
_cod_data_source_block           5aj_twin1_hklf4
_cod_database_code               7249698
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H16 F2 N O'
_chemical_oxdiff_usercomment     5aJ
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.896
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6885(9)
 0.3115(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3A-C15A \\sim C3A-C15B
 with sigma of 0.02
 C16A-C18A \\sim C16B-C18B
 with sigma of 0.04
 C15A-C16A \\sim C15B-C16B
 with sigma of 0.02
 C15A-C20A \\sim C15B-C20B
 with sigma of 0.02
 C16A-C17A \\sim C16B-C17B
 with sigma of 0.02
 C17A-C18A \\sim C17B-C18B
 with sigma of 0.02
 C18A-C19A \\sim C18B-C19B
 with sigma of 0.02
 C16A-C20A \\sim C16B-C20B
 with sigma of 0.04
 C19A-C20A \\sim C19B-C20B
 with sigma of 0.02
 C17A-C19A \\sim C17B-C19B
 with sigma of 0.04
 C18A-C20A \\sim C18B-C20B
 with sigma of 0.04
 C3A-C16A \\sim C3A-C16B
 with sigma of 0.04
 C3A-C20A \\sim C3A-C20B
 with sigma of 0.04
 C15A-C17A \\sim C15B-C17B
 with sigma of 0.04
 C15A-C19A \\sim C15B-C19B
 with sigma of 0.04
 C15-C19 \\sim C15-C1C
 with sigma of 0.04
 C15-C20 \\sim C15-C1D
 with sigma of 0.02
 C16-C17 \\sim C21-C1B
 with sigma of 0.02
 C18-C20 \\sim C18-C1D
 with sigma of 0.04
 C17-C18 \\sim C1B-C18
 with sigma of 0.02
 C15-C17 \\sim C15-C1B
 with sigma of 0.04
 C16-C18 \\sim C21-C18
 with sigma of 0.04
 C19-C20 \\sim C1C-C1D
 with sigma of 0.02
 C18-C19 \\sim C18-C1C
 with sigma of 0.02
 C15-C16 \\sim C15-C21
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 C15A, C15B, C16A, C16B, C17A, C17B, C18A, C18B, C19A, C19B, C20A, C20B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C1B, C1C, C1D, C15, C16, C17, C18, C19, C20, C21
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
5. Others
 Sof(C15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=
 Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20B)=1-FVAR(1)
 Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=FVAR(1)
 Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=Sof(H18C)=Sof(C21)=
 Sof(H21)=1-FVAR(2)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(H20)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1B(H1B), C1C(H1C), C1D(H1D), C5(H5), C5A(H5A), C6(H6), C6A(H6A), C7(H7),
 C7A(H7A), C8(H8), C8A(H8A), C9(H9), C9A(H9A), C11(H11), C11A(H11A), C12(H12),
 C12A(H12A), C13(H13), C13A(H13A), C16(H16), C16A(H16A), C16B(H16B), C17(H17),
 C17A(H17A), C17B(H17B), C18(H18), C18(H18C), C18A(H18A), C18B(H18B), C19(H19),
 C19A(H19A), C19B(H19B), C20(H20), C20A(H20A), C20B(H20B), C21(H21)
6.b Idealised Me refined as rotating group:
 C14(H14D,H14E,H14F), C14A(H14A,H14B,H14C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MiTeGEN Dual Thickness MicroLoops in  perfluoropolyether oil'
_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 1.462
_oxdiff_exptl_absorpt_empirical_full_min 0.745
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2