Iridium-Catalyzed Enantioselective Allylic Substitution of Enol Silanes from Vinylogous Esters and Amides.
Chen, Ming; Hartwig, John F.; Journal of the American Chemical Society 137 (2015) 13972–13979; doi:10.1021/jacs.5b09980

data_4129734
_publ_section_title
;
 Iridium-Catalyzed Enantioselective Allylic Substitution of Enol Silanes
 from Vinylogous Esters and Amides.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13972
_journal_page_last               13979
_journal_paper_doi               10.1021/jacs.5b09980
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_sum            'C14 H15 Br O2'
_chemical_formula_weight         295.17
_chemical_name_systematic
; 
 compound4f 
;
_space_group.centring_type       primitive
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     patterson
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2012
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.3549(4)
_cell_length_b                   14.4147(13)
_cell_length_c                   17.1170(16)
_cell_measurement_reflns_used    9992
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.33
_cell_measurement_theta_min      2.38
_cell_volume                     1321.2(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    ORTEP-32
_computing_publication_material  WinGX
_computing_structure_refinement  SHELXL-2012
_computing_structure_solution    DIRDIF-2008
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_refln_scan_rate          5
_diffrn_refln_scan_width         0.5
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15690
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.400
_diffrn_reflns_theta_min         1.847
_diffrn_source                   'microfocus sealed tube'
_exptl_absorpt_coefficient_mu    3.099
_exptl_absorpt_correction_T_max  0.862
_exptl_absorpt_correction_T_min  0.674
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.484
_exptl_crystal_description       blade
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.040
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.933
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
; 
 Flack x determined using 851 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   -0.014(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2386
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0290
_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^)+(0.0329P)^2^+1.9911P] 
 where P=(Fo^2^+2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0712
_refine_ls_wR_factor_ref         0.0730
_reflns_Friedel_coverage         0.669
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                2223
_reflns_number_total             2386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b09980_si_002.cif
_cod_data_source_block           compound4f
_cod_database_code               4129734
_shelx_estimated_absorpt_t_min   0.886
_shelx_estimated_absorpt_t_max   0.941
_shelxl_version_number           2012-9
_shelx_res_checksum              87672
_shelx_hkl_checksum              15174