Metal-free aminofluorination of α-diazo 2H-benzopyran-4-one: Convenient access to β-fluoramides
Zhang, Wentao; Sun, Minghao; You, Kejia; Pang, Yunfei; Ma, Baochun; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01089E

data_7158822
_publ_section_title
;
 Metal-free aminofluorination of \a-diazo 2H-benzopyran-4-one: Convenient
 access to \b-fluoramides
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01089E
_journal_year                    2022
_chemical_formula_moiety         'C18 H16 F N O3'
_chemical_formula_sum            'C18 H16 F N O3'
_chemical_formula_weight         313.32
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-10-26 deposited with the CCDC.	2022-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.539(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   10.6683(3)
_cell_length_b                   9.5705(3)
_cell_length_c                   30.9059(9)
_cell_measurement_reflns_used    6929
_cell_measurement_temperature    290.83(10)
_cell_measurement_theta_max      69.8430
_cell_measurement_theta_min      4.4800
_cell_volume                     3149.50(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.83(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega  101.00  175.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000    0.0000 74

  2 omega  118.00  173.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 55

  3 omega  143.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000  138.8051 27

  4 omega  132.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 46

  5 omega  115.00  158.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  150.0000 43

  6 omega   91.00  117.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   30.0000 26

  7 omega   91.00  117.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   60.0000 26

  8 omega   86.00  111.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   60.0000 25

  9 omega   86.00  112.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   30.0000 26

 10 omega   78.00  172.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 94

 11 omega   86.00  112.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  120.0000 26

 12 omega   85.00  111.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  120.0000 26

 13 omega   89.00  115.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  120.0000 26

 14 omega   88.00  114.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   90.0000 26

 15 omega   82.00  111.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  150.0000 29

 16 omega   86.00  145.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   49.0000  156.4047 59

 17 omega   82.00  108.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   70.0000   78.6532 26

 18 omega   82.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000   60.0000 25

 19 omega   82.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000   90.0000 25

 20 omega   83.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000  138.8051 26

 21 omega   78.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 25

 22 omega   80.00  105.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   73.0000  141.0602 25

 23 omega   78.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 25

 24 omega   78.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 25

 25 omega   78.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 25

 26 omega   78.00  104.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 26

 27 omega   73.00  114.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   60.0000 41

 28 omega   39.00   94.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000   60.0000 55

 29 omega   76.00  102.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   60.0000 26

 30 omega   49.00  101.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000    0.0000 52

 31 omega   34.00   60.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000   90.0000 26

 32 omega   30.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  150.0000 79

 33 omega   29.00   69.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  120.0000 40

 34 omega   25.00   53.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   60.0000 28

 35 omega   24.00   56.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   90.0000 32

 36 omega   29.00  102.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  120.0000 73

 37 omega    3.00   59.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   38.0000   90.0000 56

 38 omega   88.00  172.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -120.0000 84

 39 omega  110.00  162.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -180.0000 52

 40 omega   26.00  121.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000 -150.0000 95

 41 omega   -7.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000    0.0000 35

 42 omega  -15.00   75.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000  -90.0000 90

 43 omega   79.00  105.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000 -150.0000 26

 44 omega  -13.00   74.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000    0.0000 87

 45 omega   43.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  150.0000 66

 46 omega  -69.00  -12.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000    0.0000 57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1087328000
_diffrn_orient_matrix_UB_12      0.0016772000
_diffrn_orient_matrix_UB_13      0.0305674000
_diffrn_orient_matrix_UB_21      -0.0899319000
_diffrn_orient_matrix_UB_22      -0.0556081000
_diffrn_orient_matrix_UB_23      -0.0369605000
_diffrn_orient_matrix_UB_31      0.0319286000
_diffrn_orient_matrix_UB_32      -0.1510348000
_diffrn_orient_matrix_UB_33      0.0139463000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            26862
_diffrn_reflns_theta_full        70.10
_diffrn_reflns_theta_max         70.10
_diffrn_reflns_theta_min         4.31
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.322
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1312
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.292
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.035
_refine_ls_extinction_coef       0.00106(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     420
_refine_ls_number_reflns         5924
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0549
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0525P)^2^+0.8801P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1205
_reflns_number_gt                4726
_reflns_number_total             5924
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d2ob01089e2.cif
_cod_data_source_block           zhangwt_0309
_cod_original_cell_volume        3149.52(16)
_cod_database_code               7158822
_reflns_odcompleteness_completeness 99.95
_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 Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), N2(H2), C21(H21), C22(H22), C23(H23), C24(H24), C29(H29),
 C30(H30), C31(H31), C32(H32), C38(H38)
2.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C33(H33A,H33B,H33C), C35(H35A,H35B,
 H35C)
;
_olex2_date_sample_data_collection 2016-03-10
_olex2_submission_special_instructions 'No special instructions were received'