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_7064106
_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         'C17 H14 F3 N O4'
_chemical_formula_sum            'C17 H14 F3 N O4'
_chemical_formula_weight         353.29
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-05-27 deposited with the CCDC.	2025-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                107.418(7)
_cell_angle_beta                 97.252(7)
_cell_angle_gamma                95.632(7)
_cell_formula_units_Z            4
_cell_length_a                   7.7224(7)
_cell_length_b                   14.8067(13)
_cell_length_c                   15.0191(11)
_cell_measurement_reflns_used    2319
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      22.4020
_cell_measurement_theta_min      3.6360
_cell_volume                     1608.6(2)
_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 0.992
_diffrn_measured_fraction_theta_max 0.943
_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     56.00  86.00   1.00   10.00    --   21.29-169.00  11.00   30
  2  \w    -72.00 -46.00   1.00   10.00    --  -22.70 116.00-115.00   26
  3  \w    -23.00   7.00   1.00   10.00    --  -22.70 116.00-115.00   30
  4  \w    -88.00 -63.00   1.00   10.00    --  -22.70 169.00  28.00   25
  5  \w     -7.00  20.00   1.00   10.00    --   21.29-116.00 155.00   27
  6  \w    -49.00  43.00   1.00   10.00    --   21.29 -38.00   0.00   92
  7  \w     46.00  71.00   1.00   10.00    --   21.29-116.00 155.00   25
  8  \w      2.00  30.00   1.00   10.00    --   21.29  77.00  30.00   28
  9  \w    -97.00 -39.00   1.00   10.00    --  -22.70-178.00 120.00   58
 10  \w    -93.00  -1.00   1.00   10.00    --  -22.70 -38.00  90.00   92
;
_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  0.0603
_diffrn_reflns_av_unetI/netI     0.1365
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15647
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.564
_diffrn_reflns_theta_min         3.670
_exptl_absorpt_coefficient_mu    0.126
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87235
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.459
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.494
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.959
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     482
_refine_ls_number_reflns         8513
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.2098
_refine_ls_R_factor_gt           0.0743
_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^)+(0.0937P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.2658
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2939
_reflns_number_total             8513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03333k2.cif
_cod_data_source_block           exp_411
_cod_depositor_comments
'Adding full bibliography for 7064105--7064108.cif.'
_cod_database_code               7064106
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.942
_olex2_refinement_description
;
1. 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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C15A(H15C,H15D)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C10(H10), C13(H13), C12(H12), C10A(H10A), C11(H11), C14A(H14A),
 C11A(H11A), C12A(H12A), C13A(H13A)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F)
2.d Idealised tetrahedral OH refined as rotating group:
 O4A(H4A)
;
_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
;