Asymmetric Synthesis of Chiral Dihydrothiopyrans via an Organocatalytic Enantioselective Formal Thio [3 + 3] Cycloaddition Reaction with Binucleophilic Bisketone Thioethers.
Wang, Shengzheng; Zhang, Yongqiang; Dong, Guoqiang; Wu, Shanchao; Zhu, Shiping; Miao, Zhenyuan; Yao, Jianzhong; Li, Hao; Li, Jian; Zhang, Wannian; Sheng, Chunquan; Wang, Wei; Organic letters 15 (2013) 5570–5573; doi:10.1021/ol4027705

data_1512599
_publ_section_title
;
 Asymmetric Synthesis of Chiral Dihydrothiopyrans via an Organocatalytic
 Enantioselective Formal Thio [3 + 3] Cycloaddition Reaction with
 Binucleophilic Bisketone Thioethers.
;
_journal_issue                   21
_journal_name_full               'Organic letters'
_journal_page_first              5570
_journal_page_last               5573
_journal_paper_doi               10.1021/ol4027705
_journal_volume                  15
_journal_year                    2013
_chemical_formula_sum            'C25 H19 Br Cl N O4 S'
_chemical_formula_weight         544.83
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 104.696(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.933(3)
_cell_length_b                   6.1668(13)
_cell_length_c                   17.271(4)
_cell_measurement_reflns_used    5624
_cell_measurement_temperature    203(2)
_cell_measurement_theta_max      27.34
_cell_measurement_theta_min      2.44
_cell_volume                     1332.4(5)
_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-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      203(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0785
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            9235
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.381
_diffrn_reflns_theta_min         1.219
_exptl_absorpt_coefficient_mu    1.750
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_correction_T_min  0.267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       block
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.650
_exptl_crystal_size_mid          0.400
_exptl_crystal_size_min          0.330
_platon_squeeze_details          ' '
_refine_diff_density_max         0.523
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
; 
 Flack x determined using 1821 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.082(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         5700
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0398
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
; 
 w=1/[\s^2^(Fo^2^)+(0.0507P)^2^] 
 where P=(Fo^2^+2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1033
_refine_ls_wR_factor_ref         0.1094
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.895
_reflns_Friedel_fraction_max     0.894
_reflns_number_gt                4955
_reflns_number_total             5700
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol4027705_si_001.cif
_cod_data_source_block           compound11
_cod_database_code               1512599
_shelx_estimated_absorpt_t_min   0.396
_shelx_estimated_absorpt_t_max   0.596
_shelxl_version_number           2013-2
_shelx_res_checksum              43491
_shelx_hkl_checksum              92549