Enantioselective 6-endo bromoaminocyclization of 2,4-dienyl N-tosylcarbamates catalyzed by a chiral phosphine oxide-Sc(OTf)3 complex. A dramatic additive effect.
Huang, Hu; Pan, Hongjie; Cai, Yudong; Liu, Mao; Tian, Hua; Shi, Yian; Organic & biomolecular chemistry 13 (2015) 3566–3570; doi:10.1039/c5ob00001g

data_7154322
_publ_section_title
;
 Enantioselective 6-endo bromoaminocyclization of 2,4-dienyl
 N-tosylcarbamates catalyzed by a chiral phosphine oxide-Sc(OTf)3 complex.
 A dramatic additive effect.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3566
_journal_page_last               3570
_journal_paper_doi               10.1039/c5ob00001g
_journal_volume                  13
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H18 Br N O4 S'
_chemical_formula_sum            'C15 H18 Br N O4 S'
_chemical_formula_weight         388.27
_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   geom
_audit_block_doi                 10.5517/cc13vfzc
_audit_creation_date             2014-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2014-12-09 deposited with the CCDC.
2015-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.33(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1106(16)
_cell_length_b                   15.869(3)
_cell_length_c                   13.458(3)
_cell_measurement_reflns_used    5532
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4853
_cell_measurement_theta_min      1.5690
_cell_volume                     1670.5(6)
_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  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2013)'
_computing_structure_solution
;
'XS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      -0.0266
_diffrn_orient_matrix_UB_12      -0.0269
_diffrn_orient_matrix_UB_13      -0.1221
_diffrn_orient_matrix_UB_21      -0.0158
_diffrn_orient_matrix_UB_22      0.0679
_diffrn_orient_matrix_UB_23      -0.0329
_diffrn_orient_matrix_UB_31      0.0609
_diffrn_orient_matrix_UB_32      0.0070
_diffrn_orient_matrix_UB_33      -0.0148
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0585
_diffrn_reflns_av_unetI/netI     0.0675
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18963
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         1.569
_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  0.48329
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.544
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.138
_exptl_crystal_size_min          0.133
_refine_diff_density_max         0.754
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 2742 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.001(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         7586
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0359P)^2^+0.0091P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0998
_refine_ls_wR_factor_ref         0.1043
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                7032
_reflns_number_total             7586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ob00001g2.cif
_cod_data_source_block           sa3281b
_cod_depositor_comments
'Adding full bibliography for 7154320--7154328.cif.'
_cod_database_code               7154322
_shelxl_version_number           2013-4
_diffrn_number_total             7632
_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:
 C25(H25), C26(H26), C10(H10), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C19(H19), C21(H21), C22(H22), C27(H27), C3(H3), C4(H4), C6(H6),
 C7(H7), C12(H12)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C1(H1A,H1B,
 H1C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              46007