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_1542724
_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 N4 O3 S'
_chemical_formula_sum            'C16 H18 N4 O3 S'
_chemical_formula_weight         346.40
_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
_audit_creation_date             2015-10-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.4849(14)
_cell_length_b                   12.639(3)
_cell_length_c                   24.563(7)
_cell_measurement_reflns_used    5109
_cell_measurement_temperature    223.1500
_cell_measurement_theta_max      27.4721
_cell_measurement_theta_min      1.6581
_cell_volume                     1702.8(8)
_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      223.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 10.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.0652
              2theta: -21.3379
scan:
    Number of images: 360
               Slice: -110.0000 - 70.0000
         Image width: 0.5000
            Exp time: 10.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 45.0652
              2theta: -21.3379
;
_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      -0.0185
_diffrn_orient_matrix_UB_12      0.0252
_diffrn_orient_matrix_UB_13      -0.1796
_diffrn_orient_matrix_UB_21      -0.0309
_diffrn_orient_matrix_UB_22      -0.0725
_diffrn_orient_matrix_UB_23      -0.0070
_diffrn_orient_matrix_UB_31      -0.0373
_diffrn_orient_matrix_UB_32      0.0153
_diffrn_orient_matrix_UB_33      0.0060
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            13102
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_min         2.964
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.212
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7765
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       plate
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.325
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 1377 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3837
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0324P)^2^+0.6645P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1003
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                3715
_reflns_number_total             3837
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b03459_si_008.cif
_cod_data_source_block           sa4406
_cod_database_code               1542724
_shelxl_version_number           2013-4
_diffrn_number_total             2282
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 N4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14),
 C15(H15)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              25292
_shelx_hkl_checksum              16849
_olex2_submission_special_instructions 'No special instructions were received'