Highly Enantioselective Copper-Catalyzed Electrophilic Trifluoromethylation of β-Ketoesters
Qing-Hai Deng; Hubert Wadepohl; Lutz H. Gade; Journal of the American Chemical Society 134 (2012) 10769–10772; doi:10.1021/ja3039773

data_4118184
_publ_section_title
;
 Highly Enantioselective Copper-Catalyzed Electrophilic
 Trifluoromethylation of \b-Ketoesters
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10769
_journal_page_last               10772
_journal_paper_doi               10.1021/ja3039773
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_sum            'C15 H14 Br F3 O3'
_chemical_formula_weight         379.17
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_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     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_qd10
_audit_creation_method           SHELXL-97
_audit_update_record             'Mon Mar 12 15:48:12 CET 2012'
_cell_angle_alpha                90.00
_cell_angle_beta                 94.918(11)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   6.275(4)
_cell_length_b                   7.387(3)
_cell_length_c                   16.399(7)
_cell_measurement_reflns_used    6434
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.23
_cell_measurement_theta_min      2.49
_cell_volume                     757.4(7)
_computing_cell_refinement
;
SAINT (Bruker AXS, 1997-2008). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction        'SAINT (Bruker AXS, 1997-2008)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR2004 (Giacovazzo et al., 2004)'
_diffrn_ambient_environment      'perfluoro polyether oil'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_sigmaI/netI    0.0392
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            18760
_diffrn_reflns_theta_full        31.00
_diffrn_reflns_theta_max         32.11
_diffrn_reflns_theta_min         2.49
_diffrn_source                   'fine-focus sealed tube (Mo)'
_exptl_absorpt_coefficient_mu    2.755
_exptl_absorpt_correction_T_max  0.9278
_exptl_absorpt_correction_T_min  0.6968
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS (Sheldrick & Bruker AXS, 2004-2008)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       needle
_exptl_crystal_F_000             380
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.749
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.012(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         4950
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0386
_refine_ls_R_factor_gt           0.0310
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0301P)^2^+0.2175P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0625
_refine_ls_wR_factor_ref         0.0649
_reflns_number_gt                4479
_reflns_number_total             4950
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja3039773_si_002_1.cif
_cod_data_source_block           ga_qd10
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4118184
_audit_block_refno               1448
_audit_block_usercomment         d6-49