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_7064107
_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_absolute_configuration unk
_chemical_formula_moiety         'C20 H14 F3 N O2'
_chemical_formula_sum            'C20 H14 F3 N O2'
_chemical_formula_weight         357.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-09-04
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.27 svn.r2268, GUI svn.r4156)
;
_audit_update_record
;
2023-09-24 deposited with the CCDC.	2025-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.2062(6)
_cell_length_b                   13.1121(8)
_cell_length_c                   24.064(2)
_cell_measurement_reflns_used    1299
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.4250
_cell_measurement_theta_min      2.9660
_cell_volume                     1642.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9555
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9762
_diffrn_measured_fraction_theta_max 0.8488
_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    -84.00 -46.00   1.00   50.00    --  -18.90-178.00-180.00   38
  2  \w    -39.00  46.00   1.00   50.00    --   21.25 -77.00  30.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0884603000
_diffrn_orient_matrix_UB_12      -0.0401964000
_diffrn_orient_matrix_UB_13      0.0044276000
_diffrn_orient_matrix_UB_21      0.0583907000
_diffrn_orient_matrix_UB_22      0.0284647000
_diffrn_orient_matrix_UB_23      0.0217759000
_diffrn_orient_matrix_UB_31      -0.0847605000
_diffrn_orient_matrix_UB_32      -0.0226618000
_diffrn_orient_matrix_UB_33      0.0194521000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0974
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4701
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         28.28
_diffrn_reflns_theta_min         1.77
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.116
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.05399
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.98a (Rigaku Oxford Diffraction, 2021)
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    1.445
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.2(17)
_refine_ls_extinction_coef       0.018(3)
_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   0.999
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3431
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.1292
_refine_ls_R_factor_gt           0.0639
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0623P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1336
_refine_ls_wR_factor_ref         0.1895
_reflns_number_gt                1681
_reflns_number_total             3431
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d5nj03333k2.cif
_cod_data_source_block           exp_1224
_cod_depositor_comments
'Adding full bibliography for 7064105--7064108.cif.'
_cod_database_code               7064107
_reflns_odcompleteness_completeness 97.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 10.138
_oxdiff_exptl_absorpt_empirical_full_min 0.483