Organocatalytic Asymmetric Halogenation/Semipinacol Rearrangement: Highly Efficient Synthesis of Chiral α-Oxa-Quaternary β-Haloketones
Zhi-Min Chen; Qing-Wei Zhang; Zhi-Hua Chen; Hui Li; Yong-Qiang Tu; Fu-Min Zhang; Jin-Miao Tian; Journal of the American Chemical Society 133 (2011) 8818–8821; doi:10.1021/ja201794v

data_4106243
_publ_section_title
;
 Organocatalytic Asymmetric Halogenation/Semipinacol Rearrangement: Highly
 Efficient Synthesis of Chiral \a-Oxa-Quaternary \b-Haloketones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8818
_journal_page_last               8821
_journal_paper_doi               10.1021/ja201794v
_journal_volume                  133
_journal_year                    2011
_chemical_absolute_configuration none
_chemical_formula_sum            'C14 H13 Br O2 S2'
_chemical_formula_weight         357.27
_chemical_name_systematic
; 
 ? 
;
_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                 96.275(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   6.660(2)
_cell_length_b                   13.081(5)
_cell_length_c                   8.454(3)
_cell_measurement_reflns_used    1397
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      21.21
_cell_measurement_theta_min      2.42
_cell_volume                     732.1(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.0234
_diffrn_reflns_av_sigmaI/netI    0.0783
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            3993
_diffrn_reflns_theta_full        25.49
_diffrn_reflns_theta_max         25.49
_diffrn_reflns_theta_min         2.42
_exptl_absorpt_coefficient_mu    3.086
_exptl_absorpt_correction_T_max  0.4479
_exptl_absorpt_correction_T_min  0.4113
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       block
_exptl_crystal_F_000             360
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.31
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(1)
_refine_ls_extinction_coef       0.018(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   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     178
_refine_ls_number_reflns         2611
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0458P)^2^+0.0534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1080
_refine_ls_wR_factor_ref         0.1166
_reflns_number_gt                2055
_reflns_number_total             2611
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja201794v_si_002.cif
_cod_data_source_block           p21
_cod_original_cell_volume        732.1(5)
_cod_database_code               4106243