Silver or copper-catalyzed ring opening [3+2] annulation of 2-polyfluoroalkyl chromones/6-polyfluoroalkyl pyran-4H-ones with methylene isocyanides: regioselective synthesis of 3-polyfluoroalkyl pyrroles
Kochnev, Ivan A.; Barkov, Alexey Yu.; New Journal of Chemistry 49 (2025) 20254–20263; doi:10.1039/D5NJ03333K

data_7064105
_publ_section_title
;
 Silver or copper-catalyzed ring opening [3+2] annulation of
 2-polyfluoroalkyl chromones/6-polyfluoroalkyl pyran-4H-ones with
 methylene isocyanides: regioselective synthesis of 3-polyfluoroalkyl
 pyrroles
;
_journal_issue                   46
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              20254
_journal_page_last               20263
_journal_paper_doi               10.1039/D5NJ03333K
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C15 H11 F3 N2 O6'
_chemical_formula_sum            'C15 H11 F3 N2 O6'
_chemical_formula_weight         372.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-09-24 deposited with the CCDC.	2025-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.657(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6176(7)
_cell_length_b                   11.1985(9)
_cell_length_c                   18.9787(18)
_cell_measurement_reflns_used    2540
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      23.5470
_cell_measurement_theta_min      4.0270
_cell_volume                     1611.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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_temperature      295(2)
_diffrn_detector_area_resol_mean 16.5253
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.879
_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     68.00  93.00   1.00   60.00    --   21.29  10.00  48.00   25
  2  \w     -2.00  23.00   1.00   60.00    --   21.29  10.00  48.00   25
  3  \w     -4.00  21.00   1.00   60.00    --   21.29 -10.00-125.00   25
  4  \w    -94.00  39.00   1.00   60.00    --  -22.70 -10.00-125.00  133
  5  \w      3.00  90.00   1.00   60.00    --   21.29  57.00-120.00   87
  6  \w    -97.00 -55.00   1.00   60.00    --  -22.70-178.00  30.00   42
  7  \w    -46.00 -21.00   1.00   60.00    --  -22.70  10.00  48.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0656
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.879
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12656
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.879
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.478
_diffrn_reflns_theta_min         3.713
_exptl_absorpt_coefficient_mu    0.141
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82132
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.049
_refine_ls_extinction_coef       0.007(3)
_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   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4307
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1495
_refine_ls_R_factor_gt           0.0643
_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^)+(0.1008P)^2^+0.0865P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1690
_refine_ls_wR_factor_ref         0.2370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1880
_reflns_number_total             4307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03333k2.cif
_cod_data_source_block           exp_351
_cod_depositor_comments
'Adding full bibliography for 7064105--7064108.cif.'
_cod_database_code               7064105
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.937
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C15) \\sim Ueq, Uanis(C15A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Fixed Sof: H14A(0.5) H14B(0.5) H14C(0.5) H14D(0.5) C15(0.5) H15A(0.5)
 H15B(0.5) H15C(0.5) C15A(0.5) H15D(0.5) H15E(0.5) H15F(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C14(H14C,H14D)
4.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C15A(H15D,H15E,H15F)
;
_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
;