Hexafluoroisobutylation of enolates through a tandem elimination/allylic shift/hydrofluorination reaction
Delamare, Aline; Naulet, Guillaume; Kauffmann, Brice; Guichard, Gilles; Compain, Guillaume; Chemical Science 13 (2022) 9507–9514; doi:10.1039/D2SC02871A

data_1567479
_publ_section_title
;
 Hexafluoroisobutylation of enolates through a tandem elimination/allylic
 shift/hydrofluorination reaction
;
_journal_issue                   33
_journal_name_full               'Chemical Science'
_journal_page_first              9507
_journal_page_last               9514
_journal_paper_doi               10.1039/D2SC02871A
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C7 H4 F6 N2'
_chemical_formula_sum            'C7 H4 F6 N2'
_chemical_formula_weight         230.12
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-26 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.923(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7855(12)
_cell_length_b                   5.6753(6)
_cell_length_c                   11.6678(10)
_cell_measurement_reflns_used    1548
_cell_measurement_temperature    145
_cell_measurement_theta_max      64.4670
_cell_measurement_theta_min      3.2630
_cell_volume                     886.03(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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      145
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.984
_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   -126.00  53.00   1.00    2.00    --  -36.30   8.00  31.00  179
  2  \w   -199.00 -21.00   1.00   15.00    -- -110.00   8.00  31.00  178
  3  \w   -126.00  53.00   1.00    2.00    --  -36.30  55.00 -60.00  179
  4  \w   -126.00  53.00   1.00    2.00    --  -36.30  55.00-120.00  179
  5  \w   -126.00  53.00   1.00    2.00    --  -36.30  55.00 -30.00  179
  6  \w   -199.00 -21.00   1.00   15.00    -- -110.00  55.00 100.47  178
  7  \w   -199.00 -21.00   1.00   15.00    -- -110.00  55.00-179.48  178
  8  \w   -199.00 -21.00   1.00   15.00    -- -110.00  55.00 122.51  178
  9  \w   -199.00 -21.00   1.00   15.00    -- -110.00   9.00-180.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku FRX'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0786147000
_diffrn_orient_matrix_UB_12      0.0191626000
_diffrn_orient_matrix_UB_13      -0.0736973000
_diffrn_orient_matrix_UB_21      0.0839754000
_diffrn_orient_matrix_UB_22      -0.0315420000
_diffrn_orient_matrix_UB_23      0.1128674000
_diffrn_orient_matrix_UB_31      -0.0042363000
_diffrn_orient_matrix_UB_32      -0.2688737000
_diffrn_orient_matrix_UB_33      -0.0186241000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            5367
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.917
_diffrn_reflns_theta_min         3.303
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.790
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10409
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            clear
_exptl_crystal_colour_lustre     clear
_exptl_crystal_density_diffrn    1.725
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.366
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         1698
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0931
_refine_ls_R_factor_gt           0.0790
_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^)+(0.1574P)^2^+0.2221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2405
_refine_ls_wR_factor_ref         0.2569
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1314
_reflns_number_total             1698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02871a2.cif
_cod_data_source_block           gn_100b
_cod_depositor_comments
'Adding full bibliography for 1567476--1567479.cif.'
_cod_database_code               1567479
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.64
_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 C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C009(H009), C00B(H00C)
2.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B)
;
_shelx_res_checksum              43859
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 4.752
_oxdiff_exptl_absorpt_empirical_full_min 0.281