Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α-Fluorination of Ketenes: Synthetic and Mechanistic Studies.
Lee, Sarah Yunmi; Neufeind, Stefan; Fu, Gregory C.; Journal of the American Chemical Society 136 (2014) 8899–8902; doi:10.1021/ja5044209

data_4122019
_publ_section_title
;
 Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl
 Fluorides via the \a-Fluorination of Ketenes: Synthetic and Mechanistic
 Studies.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8899
_journal_page_last               8902
_journal_paper_doi               10.1021/ja5044209
_journal_volume                  136
_journal_year                    2014
_chemical_formula_sum            'C41.59 H60.47 B11 Cl0.7 F Fe N2 O'
_chemical_formula_weight         823.22
_chemical_name_systematic
; 
 ? 
;
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.8695(15)
_cell_length_b                   15.973(2)
_cell_length_c                   37.274(4)
_cell_measurement_reflns_used    9861
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.75
_cell_measurement_theta_min      2.49
_cell_volume                     8853.0(17)
_computing_cell_refinement       'SAINT v8.32B (Bruker-AXS, 2011)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT v8.32B (Bruker-AXS, 2011)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0679
_diffrn_reflns_av_unetI/netI     0.0776
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            65941
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.679
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.423
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6284
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.235
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3472
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.200
_refine_diff_density_max         0.511
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
; 
 Flack x determined using 4047 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   -0.006(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1586
_refine_ls_number_reflns         15615
_refine_ls_number_restraints     3857
_refine_ls_restrained_S_all      0.993
_refine_ls_R_factor_all          0.0960
_refine_ls_R_factor_gt           0.0610
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0783P)^2^+3.4672P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1563
_reflns_Friedel_coverage         0.825
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                11291
_reflns_number_total             15615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5044209_si_003.cif
_cod_data_source_block           syl004
_cod_depositor_comments
'Adding full bibliography for 4122019--4122021.cif.'
_cod_original_cell_volume        8853.2(17)
_cod_original_formula_sum        'C41.59 H60.47 B11 Cl0.70 F Fe N2 O'
_cod_database_code               4122019
_shelx_estimated_absorpt_t_min   0.849
_shelx_estimated_absorpt_t_max   0.920
_shelxl_version_number           2013-3
_shelx_res_checksum              95552
_shelx_hkl_checksum              34774