Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion.
Lu, Deng-Fu; Zhu, Cheng-Liang; Sears, Jeffrey D.; Xu, Hao; Journal of the American Chemical Society 138 (2016) 11360–11367; doi:10.1021/jacs.6b07221

data_4130826
_publ_section_title
;
 Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized
 Olefins Using Fluoride Ion.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11360
_journal_page_last               11367
_journal_paper_doi               10.1021/jacs.6b07221
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C17 H26 Fe N4 O4, 2(B F4)'
_chemical_formula_sum            'C17 H26 B2 F8 Fe N4 O4'
_chemical_formula_weight         579.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-01
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.11.25 svn.r3098 for OlexSys, GUI svn.r4951)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.2050(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.4516(9)
_cell_length_b                   13.5668(15)
_cell_length_c                   11.3680(13)
_cell_measurement_reflns_used    2923
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      30.949
_cell_measurement_theta_min      2.349
_cell_volume                     1293.2(2)
_computing_cell_refinement       'SAINT v8.32B (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.32B (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0143
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4021
_diffrn_reflns_point_group_measured_fraction_full 0.626
_diffrn_reflns_point_group_measured_fraction_max 0.623
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.366
_diffrn_reflns_theta_min         2.348
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.670
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8674
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0446 before and 0.0269 after correction.
The Ratio of minimum to maximum transmission is 0.8674.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       prism
_exptl_crystal_F_000             592
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.547
_exptl_crystal_size_mid          0.487
_exptl_crystal_size_min          0.318
_refine_diff_density_max         0.592
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.326(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     374
_refine_ls_number_reflns         3295
_refine_ls_number_restraints     236
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0748P)^2^+1.1472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1195
_refine_ls_wR_factor_ref         0.1214
_reflns_Friedel_coverage         0.237
_reflns_Friedel_fraction_full    0.254
_reflns_Friedel_fraction_max     0.250
_reflns_number_gt                3161
_reflns_number_total             3295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b07221_si_002.cif
_cod_data_source_block           1
_cod_database_code               4130826
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.711
_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
2. Restrained distances
 O3-H3B = O3-H3A
 0.975 with sigma of 0.01
 H3B-H3A
 1.55 with sigma of 0.01
 O4-H4E = O4-H4D
 0.975 with sigma of 0.01
 H4E-H4D
 1.55 with sigma of 0.01
 F8'-B2A \\sim F7'-B2A \\sim F10'-B2A \\sim F9'-B2A
 with sigma of 0.005
 F8-B2 \\sim F9-B2 \\sim F10-B2 \\sim F7-B2
 with sigma of 0.005
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(B2) = Uanis(B2A)
Uanis(F7') = Uanis(F7)
Uanis(F8) = Uanis(F8')
5. Rigid body (RIGU) restrains
 B1, F3, F4, F5, F6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 B2, F8, F9, F10, F7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 B2A, F8', F9', F10', F7'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{B2A, F7', F8', F9', F10'} sigma for 1-2: 0.02, 1-3: 0.02
as
{B2, F7, F8, F9, F10}
7. Others
 Sof(B2A)=Sof(F7')=Sof(F8')=Sof(F9')=Sof(F10')=1-FVAR(1)
 Sof(B2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C2(H2A,H2B)
8.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C9(H9)
8.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C4(H4A,H4B,H4C), C17(H17A,H17B,
 H17C), C5(H5A,H5B,H5C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'