Chiral Selenide-Catalyzed Enantioselective Allylic Reaction and Intermolecular Difunctionalization of Alkenes: Efficient Construction of C-SCF<sub>3</sub> Stereogenic Molecules.
Liu, Xiang; Liang, Yaoyu; Ji, Jieying; Luo, Jie; Zhao, Xiaodan; Journal of the American Chemical Society 140 (2018) 4782–4786; doi:10.1021/jacs.8b01513

data_4132092
_publ_section_title
;
 Chiral Selenide-Catalyzed Enantioselective Allylic Reaction and
 Intermolecular Difunctionalization of Alkenes: Efficient Construction of
 C-SCF<sub>3</sub> Stereogenic Molecules.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4782
_journal_page_last               4786
_journal_paper_doi               10.1021/jacs.8b01513
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C19 H19 Br F3 N O2 S2'
_chemical_formula_sum            'C19 H19 Br F3 N O2 S2'
_chemical_formula_weight         494.38
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.819(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.1930(2)
_cell_length_b                   7.5099(2)
_cell_length_c                   13.7839(2)
_cell_measurement_reflns_used    9744
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0600
_cell_measurement_theta_min      4.4540
_cell_volume                     1024.59(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 21.1652
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00 120.00  100
  2  \w   -116.00 -18.00   1.00    1.00    --  -42.02 -37.00 150.00   98
  3  \w   -130.00  46.00   1.00    1.00    --  -42.02   0.00 -90.00  176
  4  \w   -118.00  -9.00   1.00    1.00    --  -42.02 -77.00-150.00  109
  5  \w     23.00  98.00   1.00    1.00    --   42.02-125.00-180.00   75
  6  \w     18.00 116.00   1.00    1.00    --   42.02  37.00 120.00   98
  7  \w     79.00 178.00   1.00    1.00    --  107.79  61.00 120.00   99
  8  \w     35.00 134.00   1.00    1.00    --  107.79 -45.00 -30.00   99
  9  \w     82.00 178.00   1.00    1.00    --  107.79  45.00-180.00   96
 10  \w     75.00 178.00   1.00    1.00    --  107.79  77.00 150.00  103
 11  \w     79.00 178.00   1.00    1.00    --  107.79  61.00-120.00   99
 12  \w     94.00 178.00   1.00    1.00    --  107.79 125.00 -60.00   84
 13  \w     75.00 178.00   1.00    1.00    --  107.79  77.00 120.00  103
 14  \w     75.00 178.00   1.00    1.00    --  107.79  77.00-180.00  103
 15  \w     35.00 122.00   1.00    1.00    --  107.79-125.00 -30.00   87
 16  \w     79.00 178.00   1.00    1.00    --  107.79  61.00 150.00   99
 17  \w     75.00 178.00   1.00    1.00    --  107.79  77.00  90.00  103
 18  \w     79.00 178.00   1.00    1.00    --  107.79  61.00-150.00   99
 19  \w     79.00 178.00   1.00    1.00    --  107.79  61.00-180.00   99
 20  \w     82.00 178.00   1.00    1.00    --  107.79  45.00-120.00   96
 21  \w     82.00 178.00   1.00    1.00    --  107.79  45.00 150.00   96
 22  \w     75.00 178.00   1.00    1.00    --  107.79  77.00-150.00  103
 23  \w     75.00 178.00   1.00    1.00    --  107.79  77.00-120.00  103
 24  \w     25.00 109.00   1.00    1.00    --  107.79 -94.00-120.00   84
 25  \w   -118.00  -9.00   1.00    1.00    --  -42.02 -77.00  60.00  109
 26  \w   -118.00  -9.00   1.00    1.00    --  -42.02 -77.00 -30.00  109
 27  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00-120.00  100
 28  \w    -66.00  32.00   1.00    1.00    --  -42.02  37.00 -90.00   98
 29  \w     23.00  98.00   1.00    1.00    --   42.02-125.00   0.00   75
 30  \w     80.00 162.00   1.00    1.00    --  107.79  30.00  30.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0642828000
_diffrn_orient_matrix_UB_12      -0.0642723000
_diffrn_orient_matrix_UB_13      0.0842078000
_diffrn_orient_matrix_UB_21      0.1401687000
_diffrn_orient_matrix_UB_22      -0.0000489000
_diffrn_orient_matrix_UB_23      0.0733213000
_diffrn_orient_matrix_UB_31      -0.0212076000
_diffrn_orient_matrix_UB_32      0.1948367000
_diffrn_orient_matrix_UB_33      0.0278106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18342
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.173
_diffrn_reflns_theta_min         4.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.024
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47762
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.602
_exptl_crystal_description       needle
_exptl_crystal_F_000             500
_exptl_crystal_size_max          0.9
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.150
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.165
_refine_ls_abs_structure_details
;
 Flack x determined using 1627 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         3964
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0612
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1190P)^2^+4.2580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1960
_refine_ls_wR_factor_ref         0.1972
_reflns_Friedel_coverage         0.772
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                3866
_reflns_number_total             3964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b01513_si_003.cif
_cod_data_source_block           17010403
_cod_database_code               4132092
_chemical_oxdiff_formula         'C H O N S Br F'
_chemical_oxdiff_usercomment     LX
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 C(H,H,H) groups
2. Restrained distances
 C9-C10
 1.39 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C5(H5A,H5B), C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C18(H18), C19(H19), C11(H11), C15(H15), C12(H12), C8(H8), C9(H9),
 C14(H14)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.845
_oxdiff_exptl_absorpt_empirical_full_min 0.603