Rhodium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic Tertiary Allylic Trichloroacetimidates with Anilines
Jeffrey S. Arnold; Hien M. Nguyen; Journal of the American Chemical Society 134 (2012) 8380–8383; doi:10.1021/ja302223p

data_4117962
_publ_section_title
;
 Rhodium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic
 Tertiary Allylic Trichloroacetimidates with Anilines
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8380
_journal_page_last               8383
_journal_paper_doi               10.1021/ja302223p
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_moiety         '(C18 H21 N O Br)+, (C2 O2 F3)- '
_chemical_formula_sum            'C20 H21 Br F3 N O3'
_chemical_formula_weight         460.29
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 101.940(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.7144(12)
_cell_length_b                   8.8267(10)
_cell_length_c                   20.144(3)
_cell_measurement_reflns_used    9554
_cell_measurement_temperature    190(2)
_cell_measurement_theta_max      27.9
_cell_measurement_theta_min      1.0
_cell_volume                     2037.8(4)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor, 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction
'HKL denzo, Scalepack (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'SHELXTL v6.1 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.1 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXTL v6.1 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL v6.1 (Sheldrick, 2008)'
_diffrn_ambient_temperature      190(2)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       'CCD phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_sigmaI/netI    0.0323
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            57173
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         27.5
_diffrn_reflns_theta_min         2.9
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.064
_exptl_absorpt_correction_T_max  0.8862
_exptl_absorpt_correction_T_min  0.5077
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'HKL Scalepack (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       plate
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.360
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.004(5)
_refine_ls_extinction_coef       0.0020(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     530
_refine_ls_number_reflns         9061
_refine_ls_number_restraints     139
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0344
_refine_ls_shift/su_max          0.022
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0370P)^2^+0.6079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0744
_refine_ls_wR_factor_ref         0.0795
_reflns_number_gt                7601
_reflns_number_total             9061
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja302223p_si_001.cif
_cod_data_source_block           ngu122
_cod_original_sg_symbol_Hall     'P 2yb '
_cod_original_sg_symbol_H-M      'P 21 '
_cod_database_code               4117962