Highly Enantioselective Chlorination of β-Keto Esters and Subsequent SN2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers
Kazutaka Shibatomi; Yoshinori Soga; Akira Narayama; Ikuhide Fujisawa; Seiji Iwasa; Journal of the American Chemical Society 134 (2012) 9836–9839; doi:10.1021/ja304806j

data_4118114
_publ_section_title
;
 Highly Enantioselective Chlorination of \b-Keto Esters and Subsequent SN2
 Displacement of Tertiary Chlorides: A Flexible Method for the
 Construction of Quaternary Stereogenic Centers
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9836
_journal_page_last               9839
_journal_paper_doi               10.1021/ja304806j
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C33 H25 F12 N O5, C2 H3 N'
_chemical_formula_sum            'C35 H28 F12 N2 O5'
_chemical_formula_weight         784.59
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yab'
_symmetry_space_group_name_H-M   'P 1 21/a 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                 94.60(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.124(5)
_cell_length_b                   17.671(10)
_cell_length_c                   22.813(16)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      34.94
_cell_measurement_theta_min      30.48
_cell_volume                     3666(4)
_computing_cell_refinement       'Rigaku WinAFC'
_computing_data_collection       'Rigaku WinAFC'
_computing_data_reduction        'Rigaku WinAFC'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'
_computing_publication_material  'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      298(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku AFC-7R'
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_R_equivalents  0.0184
_diffrn_reflns_av_sigmaI/netI    0.0430
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       0
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            8457
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         2.52
_diffrn_source                   'Rotating Anode'
_diffrn_standards_interval_count 150
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.130
_exptl_absorpt_correction_T_max  0.9871
_exptl_absorpt_correction_T_min  0.9029
_exptl_absorpt_correction_type   psi-scan
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       platelet
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.80
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.176
_refine_diff_density_min         -0.128
_refine_diff_density_rms         0.028
_refine_ls_extinction_coef       0.0029(3)
_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   1.012
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     664
_refine_ls_number_reflns         6457
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1006
_refine_ls_R_factor_gt           0.0387
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0376P)^2^+0.7029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0868
_refine_ls_wR_factor_ref         0.1126
_reflns_number_gt                3556
_reflns_number_total             6457
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja304806j_si_004.cif
_cod_data_source_block           shib41
_cod_original_sg_symbol_H-M      'P 21/a'
_cod_database_code               4118114