Phosphine Oxide-Sc(OTf)3 Catalyzed Highly Regio- and Enantioselective Bromoaminocyclization of (E)-Cinnamyl Tosylcarbamates. An Approach to a Class of Synthetically Versatile Functionalized Molecules.
Pan, Hongjie; Huang, Hu; Liu, Weigang; Tian, Hua; Shi, Yian; Organic letters 18 (2016) 896–; doi:10.1021/acs.orglett.5b03459

data_1542722
_publ_section_title
;
 Phosphine Oxide-Sc(OTf)3 Catalyzed Highly Regio- and Enantioselective
 Bromoaminocyclization of (E)-Cinnamyl Tosylcarbamates. An Approach to a
 Class of Synthetically Versatile Functionalized Molecules.
;
_journal_issue                   5
_journal_name_full               'Organic letters'
_journal_page_first              896
_journal_paper_doi               10.1021/acs.orglett.5b03459
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H13 Br F3 N O4 S'
_chemical_formula_sum            'C17 H13 Br F3 N O4 S'
_chemical_formula_weight         464.25
_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     direct
_audit_creation_date             2015-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.600(4)
_cell_length_b                   14.941(4)
_cell_length_c                   16.318(4)
_cell_measurement_reflns_used    12678
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      31.5152
_cell_measurement_theta_min      1.8481
_cell_volume                     3559.6(16)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.1005
              2theta: -20.1287
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 15.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.1005
              2theta: -20.1287
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.0272
_diffrn_orient_matrix_UB_12      0.0444
_diffrn_orient_matrix_UB_13      0.0444
_diffrn_orient_matrix_UB_21      0.0015
_diffrn_orient_matrix_UB_22      -0.0478
_diffrn_orient_matrix_UB_23      0.0468
_diffrn_orient_matrix_UB_31      0.0562
_diffrn_orient_matrix_UB_32      -0.0162
_diffrn_orient_matrix_UB_33      -0.0183
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            28297
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.503
_diffrn_reflns_theta_min         1.872
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.481
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7607
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.733
_exptl_crystal_description       block
_exptl_crystal_F_000             1856
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Flack x determined using 2407 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         8164
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0318P)^2^+6.6530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1141
_refine_ls_wR_factor_ref         0.1206
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                7342
_reflns_number_total             8164
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b03459_si_004.cif
_cod_data_source_block           sa4178
_cod_original_cell_volume        3559.6(15)
_cod_database_code               1542722
_diffrn_number_total             4565
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C1A(H1A), C2A(H2A)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C3A(H3AA,H3AB)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C12(H12), C13(H13), C15(H15), C16(H16), C7A(H7A), C9A(H9A),
 C12A(H12A), C13A(H13A), C15A(H15A), C16A(H16A)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              89649
_shelx_hkl_checksum              97675
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'