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_4122020
_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         'C12 H15 Br F N O'
_chemical_formula_sum            'C12 H15 Br F N O'
_chemical_formula_weight         288.16
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-07-31
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.193(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.4495(7)
_cell_length_b                   5.1247(4)
_cell_length_c                   14.4009(12)
_cell_measurement_reflns_used    4500
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.596
_cell_measurement_theta_min      2.420
_cell_volume                     621.02(9)
_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 0.997
_diffrn_measured_fraction_theta_max 0.994
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23534
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.420
_exptl_absorpt_coefficient_mu    3.301
_exptl_absorpt_correction_T_max  0.862085
_exptl_absorpt_correction_T_min  0.634353
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0924 before and 0.0763 after correction.
 The Ratio of minimum to maximum transmission is 0.74.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 23534 reflections, Rint = 0.0432
 (14358 with I > 3sig(I), Rint = 0.0381)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.541
_exptl_crystal_F_000             292
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.659
_refine_diff_density_min         -0.544
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 987 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.021(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         2470
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0379P)^2^+0.7929P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0842
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.775
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                2404
_reflns_number_total             2470
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5044209_si_002.cif
_cod_data_source_block           syl003
_cod_depositor_comments
'Adding full bibliography for 4122019--4122021.cif.'
_cod_database_code               4122020
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C9(H9), C8(H8), C11(H11), C12(H12)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C3(H3A,H3B,H3C), C6(H6A,H6B,H6C)
;
_shelxl_version_number           2013-2