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_1567476
_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_absolute_configuration ad
_chemical_formula_moiety         'C31 H25 F6 N3 Ni O3, C31 H24 F6.099 N3 Ni O3'
_chemical_formula_sum            'C62 H49 F12.1 N6 Ni2 O6'
_chemical_formula_weight         1321.34
_chemical_name_systematic        gc43
_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     dual
_audit_creation_date             2020-04-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.01.31 svn.r88ba2a32 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-02-26 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4863(2)
_cell_length_b                   16.5824(3)
_cell_length_c                   22.2267(2)
_cell_measurement_reflns_used    36219
_cell_measurement_temperature    130
_cell_measurement_theta_max      73.7090
_cell_measurement_theta_min      2.6330
_cell_volume                     5707.82(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      130
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.980
_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   -193.00 -13.00   1.00   10.00    -- -103.00  24.00-144.00  180
  2  \w   -124.00  56.00   1.00    2.00    --  -34.00  60.00 144.00  180
  3  \w   -193.00 -13.00   1.00   10.00    -- -103.00  60.00 144.00  180
  4  \w   -193.00 -36.00   1.00   10.00    -- -103.00  60.00 -72.00  157
  5  \w   -193.00 -13.00   1.00   10.00    -- -103.00  60.00-144.00  180
  6  \w   -124.00  56.00   1.00    2.00    --  -34.00  36.00-180.00  180
  7  \w   -173.00 -83.00   1.00   10.00    -- -103.00  24.00 -36.00   90
  8  \w   -140.00 -34.00   1.00   10.00    -- -103.00  48.00-108.00  106
  9  \w   -193.00-148.00   1.00   10.00    -- -103.00  36.00-180.00   45
;
_diffrn_measurement_device       'abstract 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      -0.0296346000
_diffrn_orient_matrix_UB_12      0.0450572000
_diffrn_orient_matrix_UB_13      0.0569612000
_diffrn_orient_matrix_UB_21      0.0853467000
_diffrn_orient_matrix_UB_22      -0.0223334000
_diffrn_orient_matrix_UB_23      0.0313664000
_diffrn_orient_matrix_UB_31      0.0415237000
_diffrn_orient_matrix_UB_32      0.0781995000
_diffrn_orient_matrix_UB_33      -0.0239357000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0178
_diffrn_reflns_av_unetI/netI     0.0112
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            41119
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.339
_diffrn_reflns_theta_min         3.325
_diffrn_source                   'Rigaku FRX'
_diffrn_source_type              'Rotating anode (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.626
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.538
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.527
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 4598 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(7)
_refine_ls_extinction_coef       0.00094(5)
_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   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     870
_refine_ls_number_reflns         10949
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0308
_refine_ls_R_factor_gt           0.0307
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0388P)^2^+3.5224P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0810
_refine_ls_wR_factor_ref         0.0810
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    0.929
_reflns_Friedel_fraction_max     0.892
_reflns_number_gt                10922
_reflns_number_total             10949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02871a2.cif
_cod_data_source_block           gc_43_f
_cod_depositor_comments
'Adding full bibliography for 1567476--1567479.cif.'
_cod_original_formula_sum        'C62 H49 F12.10 N6 Ni2 O6'
_cod_database_code               1567476
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C31 H25 F6 N3 O3 Ni'
_shelx_estimated_absorpt_t_max   0.854
_shelx_estimated_absorpt_t_min   0.854
_reflns_odcompleteness_completeness 98.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.17
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F2-C5 \\sim F1-C5
 with sigma of 0.02
 F4-C5 \\sim F3-C5
 with sigma of 0.02
 C5-F6 \\sim C5-F5
 with sigma of 0.02
 F16-C02A \\sim F13-C0AA
 with sigma of 0.02
 F15-C02A \\sim F11-C0AA
 with sigma of 0.02
 C014-C02A \\sim C014-C0AA
 with sigma of 0.02
 F1Z-C02A \\sim F14-C0AA
 with sigma of 0.02
 F16-F15 \\sim F13-F11
 with sigma of 0.04
 F16-C014 \\sim F13-C014
 with sigma of 0.04
 F16-F1Z \\sim F13-F14
 with sigma of 0.04
 F15-C014 \\sim F11-C014
 with sigma of 0.04
 F15-F1Z \\sim F11-F14
 with sigma of 0.04
 C014-F1Z \\sim C014-F14
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C01L
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F4, F2, F6, F3, F1, F5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01L, C5, F4, F2, F6, F3, F1, F5
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 F3, F5, F4, F6, F1, F2, C5
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 F14, F11, C0AA, F13, C02A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F3)=Sof(F1)=Sof(F5)=1-FVAR(1)
 Sof(F4)=Sof(F2)=Sof(F6)=FVAR(1)
 Sof(F13)=Sof(F11)=Sof(F14)=Sof(C0AA)=1-FVAR(2)
 Sof(F16)=Sof(F15)=Sof(F1Z)=Sof(C02A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C01M(H01M), C01R(H01R), C01X(H01X), C013(H013)
5.b Secondary CH2 refined with riding coordinates:
 C00Y(H00A,H00B), C01C(H01H,H01J), C01E(H01A,H01B), C01Q(H01C,H01D), C01W(H01E,
 H01F), C018(H01P,H01Q), C022(H02A,H02E), C023(H02F,H02G), C024(H02H,H02I),
 C026(H02J,H02K)
5.c Aromatic/amide H refined with riding coordinates:
 C00Q(H00Q), C00S(H00S), C00V(H00V), C00X(H00X), C01A(H01G), C01D(H01K),
 C01F(H01L), C01I(H01I), C01J(H01O), C01N(H01N), C01S(H01S), C01T(H01T),
 C01U(H01U), C02B(H02B), C02C(H02C), C02D(H02D), C010(H010), C011(H011),
 C015(H015), C016(H016), C017(H017), C020(H020), C025(H025), C027(H027),
 C028(H028)
;
_shelx_res_checksum              68530
_olex2_submission_original_sample_id gc43
_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 1.612
_oxdiff_exptl_absorpt_empirical_full_min 0.696