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_4121573
_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 ad
_chemical_formula_moiety         'C27 H22 Cl F O, C0.58 H1.16 Cl1.16'
_chemical_formula_sum            'C27.58 H23.16 Cl2.16 F O'
_chemical_formula_weight         466.24
_chemical_name_systematic
;
 ?
;
_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             2013-08-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.076(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.4485(6)
_cell_length_b                   5.9142(3)
_cell_length_c                   17.0352(8)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.48
_cell_measurement_theta_min      2.16
_cell_volume                     1153.23(10)
_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
;
XS, 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 0.955
_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  0.0601
_diffrn_reflns_av_unetI/netI     0.0730
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            62094
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         37.564
_diffrn_reflns_theta_min         1.779
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.326
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       needle
_exptl_crystal_F_000             484.8
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.818
_refine_diff_density_min         -0.637
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 3069 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.005(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.957
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     321
_refine_ls_number_reflns         11432
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0717P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1290
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                8151
_reflns_number_total             11432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja501815p_si_005.cif
_cod_data_source_block           crystal_005
_cod_depositor_comments
'Adding full bibliography for 4121570--4121574.cif.'
_cod_database_code               4121573
_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. Restrained distances
 C28-Cl2 \\sim C28-Cl3A \\sim C28-Cl3B \\sim C28-Cl3C
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl3A \\sim Cl3B \\sim Cl3C \\sim Cl2 \\sim C28: within 3.2A with sigma of 0.01 and sigma for terminal atoms of 0.005
4. Others
 1*[Sof(Cl3A)]+1*[Sof(Cl3B)]+1*[Sof(Cl3C)]-1*[Sof(Cl2)+Sof(C28)+Sof(H28A)+
 Sof(H28B)]=0 with esd of 0.0001
 Sof(Cl2)=Sof(C28)=Sof(H28A)=Sof(H28B)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C28(H28A,H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27)
5.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelxl_version_number           2013-2