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_1542723
_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         'C16 H18 Br N O3 S'
_chemical_formula_sum            'C16 H18 Br N O3 S'
_chemical_formula_weight         384.28
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.460(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.9781(18)
_cell_length_b                   19.198(6)
_cell_length_c                   7.657(2)
_cell_measurement_reflns_used    2783
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4785
_cell_measurement_theta_min      2.1216
_cell_volume                     833.6(4)
_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 0.988
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.0986
              2theta: -19.9761
scan:
    Number of images: 330
               Slice: -110.0000 - 55.0000
         Image width: 0.5000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.0986
              2theta: -19.9761
scan:
    Number of images: 328
               Slice: -110.0000 - 54.0000
         Image width: 0.5000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 90.0000
                 XTD: 45.2416
              2theta: -19.8995
;
_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      0.1678
_diffrn_orient_matrix_UB_12      0.0532
_diffrn_orient_matrix_UB_13      0.0103
_diffrn_orient_matrix_UB_21      0.0011
_diffrn_orient_matrix_UB_22      0.0065
_diffrn_orient_matrix_UB_23      -0.0517
_diffrn_orient_matrix_UB_31      0.0014
_diffrn_orient_matrix_UB_32      0.1366
_diffrn_orient_matrix_UB_33      0.0173
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            8809
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.497
_diffrn_reflns_theta_min         2.999
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.602
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       block
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.394
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.012(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3548
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0290
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0299P)^2^+0.1872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0671
_refine_ls_wR_factor_ref         0.0678
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                3449
_reflns_number_total             3548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b03459_si_006.cif
_cod_data_source_block           sa4201
_cod_database_code               1542723
_diffrn_number_total             1960
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.988(9) 0.012(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3.a Riding coordinates:
 O3(H3), N1(H1)
3.b Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2)
3.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
3.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15)
3.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              93884
_shelx_hkl_checksum              96635
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'