Organocatalytic Cascade Sulfa-Michael/Aldol Reaction of β,β-Disubstituted Enones: Enantioselective Synthesis of Tetrahydrothiophenes with a Trifluoromethylated Quaternary Center
Yu Su; Jun-Bing Ling; Shuang Zhang; Peng-Fei Xu; Journal of Organic Chemistry 78 (2013) 11053–11058; doi:10.1021/jo4016024

data_4028697
_publ_contact_author_name
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;
_publ_section_title
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 Organocatalytic Cascade Sulfa-Michael/Aldol Reaction of
 \b,\b-Disubstituted Enones: Enantioselective Synthesis of
 Tetrahydrothiophenes with a Trifluoromethylated Quaternary Center
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_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              11053
_journal_page_last               11058
_journal_paper_doi               10.1021/jo4016024
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H15 F3 O2 S'
_chemical_formula_sum            'C18 H15 F3 O2 S'
_chemical_formula_weight         352.36
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-04-09
_audit_creation_method
;
  Olex2 1.2
  (compiled Mar 21 2013 11:16:32, GUI svn.r4446)
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_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.5555(3)
_cell_length_b                   10.1638(4)
_cell_length_c                   19.3090(8)
_cell_measurement_reflns_used    1593
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.0560
_cell_measurement_theta_min      4.1360
_cell_volume                     1679.04(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9960
_diffrn_measured_fraction_theta_max 0.8361
_diffrn_measurement_details
;
  1 omega  -87.00  -60.60   1.2000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000  -60.0000 22

  2 omega    9.00   87.00   1.2000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  150.0000 65

  3 omega  -17.00   56.20   1.2000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -38.0000 -180.0000 61
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0254656000
_diffrn_orient_matrix_UB_12      -0.0067881000
_diffrn_orient_matrix_UB_13      -0.0347648000
_diffrn_orient_matrix_UB_21      0.0666009000
_diffrn_orient_matrix_UB_22      0.0390510000
_diffrn_orient_matrix_UB_23      0.0074571000
_diffrn_orient_matrix_UB_31      0.0422882000
_diffrn_orient_matrix_UB_32      -0.0574600000
_diffrn_orient_matrix_UB_33      0.0092024000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            5132
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         3.11
_diffrn_source                   'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.231
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98082
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.153
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.02(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.931
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3272
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.931
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0504
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1707
_reflns_number_gt                2283
_reflns_number_total             3272
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4016024_si_001.cif
_cod_data_source_block           suyu0408
_cod_database_code               4028697
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
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