Transition-metal free selective C(α)–C(β) bond cleavage of trifluoromethyl ketones with amidines under air: facile access to 5-trifluoromethylated Imidazol-4-ones
Zhu, Chuanle; Liu, Chi; Zeng, Hao; Chen, Fulin; Jiang, Huanfeng; Organic Chemistry Frontiers 6 (2019) 858–; doi:10.1039/C9QO00029A

data_1554705
_publ_section_title
;
 Transition-metal free selective C(\a)--C(\b) bond cleavage of
 trifluoromethyl ketones with amidines under air: facile access to
 5-trifluoromethylated Imidazol-4-ones
;
_journal_issue                   6
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              858
_journal_paper_doi               10.1039/C9QO00029A
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety         'C16 H11 F3 N2 O'
_chemical_formula_sum            'C16 H11 F3 N2 O'
_chemical_formula_weight         304.27
_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             2018-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-06-06 deposited with the CCDC.
2019-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.268(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.59270(10)
_cell_length_b                   24.4163(4)
_cell_length_c                   9.1339(2)
_cell_measurement_reflns_used    3056
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.9160
_cell_measurement_theta_min      5.3860
_cell_volume                     1396.18(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_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    -48.00 -17.00   1.00    1.00    --  -41.11 -57.00   0.00   31
  2  \w   -102.00 -58.00   1.00    1.00    --  -41.11 -57.00   0.00   44
  3  \w     24.00  88.00   1.00    1.00    --   41.11-125.00 -90.00   64
  4  \w     37.00 133.00   1.00    1.00    --  106.95 -77.00-150.00   96
  5  \w     62.00 178.00   1.00    1.00    --  106.95  15.00 -90.00  116
  6  \w    152.00 178.00   1.00    1.00    --  106.95 125.00 -30.00   26
  7  \w     94.00 164.00   1.00    1.00    --  106.95 125.00 -90.00   70
  8  \w     32.00 116.00   1.00    1.00    --  106.95 -30.00-150.00   84
  9  \w   -112.00 -21.00   1.00    1.00    --  -41.11 -38.00  90.00   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0858470000
_diffrn_orient_matrix_UB_12      0.0265751000
_diffrn_orient_matrix_UB_13      -0.1607017000
_diffrn_orient_matrix_UB_21      -0.0047751000
_diffrn_orient_matrix_UB_22      0.0561472000
_diffrn_orient_matrix_UB_23      0.0758203000
_diffrn_orient_matrix_UB_31      0.2304463000
_diffrn_orient_matrix_UB_32      0.0110302000
_diffrn_orient_matrix_UB_33      0.0010886000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5053
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.527
_diffrn_reflns_theta_min         3.621
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.028
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.448
_exptl_crystal_description       block
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         2717
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0517
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0802P)^2^+0.2505P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1251
_refine_ls_wR_factor_ref         0.1316
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2430
_reflns_number_total             2717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00029a2.cif
_cod_data_source_block           1693-3
_cod_database_code               1554705
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C9(H9), C15(H15), C13(H13), C5(H5), C14(H14), C8(H8),
 C7(H7), C6(H6)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.299
_oxdiff_exptl_absorpt_empirical_full_min 0.591