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_4121574
_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         'C22 H19 F O2'
_chemical_formula_sum            'C22 H19 F O2'
_chemical_formula_weight         334.37
_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
_audit_creation_date             2013-08-14
_audit_creation_method
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  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.86120(10)
_cell_length_b                   15.7648(3)
_cell_length_c                   18.3237(13)
_cell_measurement_reflns_used    52384
_cell_measurement_temperature    93
_cell_measurement_theta_max      68.3
_cell_measurement_theta_min      2.4
_cell_volume                     1693.12(13)
_computing_cell_refinement
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CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)
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_computing_data_collection
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CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)
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_computing_data_reduction
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CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)
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_computing_molecular_graphics
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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
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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
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_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      93
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2222
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device
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AFC11 (Left): Eulerian 3 circle
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Rigaku Saturn944+ (2x2 bin mode)
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_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support Unknown
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.058758
_diffrn_orient_matrix_UB_12      -0.022814
_diffrn_orient_matrix_UB_13      0.047327
_diffrn_orient_matrix_UB_21      0.105585
_diffrn_orient_matrix_UB_22      -0.049578
_diffrn_orient_matrix_UB_23      -0.004277
_diffrn_orient_matrix_UB_31      0.120451
_diffrn_orient_matrix_UB_32      0.032330
_diffrn_orient_matrix_UB_33      0.026837
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            58234
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.208
_diffrn_reflns_theta_min         3.699
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku, 2009)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       Block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.109
_refine_diff_density_min         -0.166
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1266 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3085
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0238
_refine_ls_R_factor_gt           0.0237
_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^)+(0.0283P)^2^+0.3398P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0599
_refine_ls_wR_factor_ref         0.0600
_reflns_Friedel_coverage         0.707
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.001
_reflns_number_gt                3066
_reflns_number_total             3085
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja501815p_si_002.cif
_cod_data_source_block           yfl02
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/usr/data/users/saulius/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 

 Adding full bibliography for 4121570--4121574.cif.
;
_cod_original_formula_sum        'C22 H19 F1 O2 '
_cod_database_code               4121574
_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 C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_shelxl_version_number           2013-2