Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones.
Liang, Yufan; Fu, Gregory C.; Journal of the American Chemical Society 136 (2014) 5520–5524; doi:10.1021/ja501815p

data_4121571
_publ_section_title
;
 Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi
 Cross-Couplings of Racemic \a,\a-Dihaloketones.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5520
_journal_page_last               5524
_journal_paper_doi               10.1021/ja501815p
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C24 H23 F O'
_chemical_formula_sum            'C24 H23 F O'
_chemical_formula_weight         346.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-08-19
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.639(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.777(6)
_cell_length_b                   15.082(5)
_cell_length_c                   15.600(6)
_cell_measurement_reflns_used    5030
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.86
_cell_measurement_theta_min      2.59
_cell_volume                     3694(2)
_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 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1056
_diffrn_reflns_av_unetI/netI     0.1027
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25299
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.357
_diffrn_reflns_theta_min         1.395
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1982 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).

The absolute stereochemistry cannot be determined from the diffraction data. 
The absolute stereochemistry was assigned by reference to the chiral center 
present in the starting material. 
;
_refine_ls_abs_structure_Flack   -0.5(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     471
_refine_ls_number_reflns         7544
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.1120
_refine_ls_R_factor_gt           0.0797
_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^)+(0.0481P)^2^+11.5801P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1624
_refine_ls_wR_factor_ref         0.1746
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5419
_reflns_number_total             7544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja501815p_si_004.cif
_cod_data_source_block           crystal_004
_cod_depositor_comments
'Adding full bibliography for 4121570--4121574.cif.'
_cod_database_code               4121571
_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 O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C12(H12A,H12B), C9B(H9BA,H9BB), C12B(H12C,H12D)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C4B(H4B), C5B(H5B), C6B(H6B), C7B(H7B), C8B(H8B), C10B(H10B), C14B(H14B),
 C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B), C20B(H20B), C21B(H21B),
 C22B(H22B), C23B(H23B), C24B(H24B)
2.c X=CH2 refined with riding coordinates:
 C11(H11A,H11B), C11B(H11C,H11D)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1B(H1B)
;
_shelxl_version_number           2013-2