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_4122021
_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_absolute_configuration ad
_chemical_formula_moiety         'C16 H15 Cl F N O'
_chemical_formula_sum            'C16 H15 Cl F N O'
_chemical_formula_weight         291.74
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_symmetry_cell_setting           hexagonal
_symmetry_space_group_name_Hall  'P 61'
_symmetry_space_group_name_H-M   'P 61'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             2013-07-02
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   21.7099(11)
_cell_length_b                   21.7099(11)
_cell_length_c                   5.3925(3)
_cell_measurement_reflns_used    9900
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.45
_cell_measurement_theta_min      2.87
_cell_volume                     2201.1(2)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0653
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            51350
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.120
_diffrn_reflns_theta_min         1.876
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.266
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8720
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0662 before and 0.0617 after correction.
The Ratio of minimum to maximum transmission is 0.8720.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
Density corresponding to approximately 24 electrons per unit cell could not 
be modeled in a chemically reasonable manner and was removed using 
Platon/Squeeze, leaving voids totaling 166 cubic angstroms. The use of 
Squeeze did not change the interpretation of the absolute stereochemistry.
;
_refine_diff_density_max         0.376
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2031 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         6146
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0560P)^2^+0.0843P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0989
_reflns_Friedel_coverage         0.798
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                5108
_reflns_number_total             6146
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5044209_si_001.cif
_cod_data_source_block           syl002-sr
_cod_depositor_comments
'Adding full bibliography for 4122019--4122021.cif.'
_cod_original_cell_volume        2201.1(3)
_cod_original_sg_symbol_H-M      'p 61'
_cod_database_code               4122021
_olex2_refinement_description
;
;
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.906
_shelxl_version_number           2013-2