Enantioselective 6-exo-Bromoaminocyclization of Homoallylic N-Tosylcarbamates Catalyzed by a Novel Monophosphine-Sc(OTf)3 Complex.
Liu, Weigang; Pan, Hongjie; Tian, Hua; Shi, Yian; Organic letters 17 (2015) 3956–3959; doi:10.1021/acs.orglett.5b01779

data_1555126
_publ_section_title
;
 Enantioselective 6-exo-Bromoaminocyclization of Homoallylic
 N-Tosylcarbamates Catalyzed by a Novel Monophosphine-Sc(OTf)3 Complex.
;
_journal_issue                   16
_journal_name_full               'Organic letters'
_journal_page_first              3956
_journal_page_last               3959
_journal_paper_doi               10.1021/acs.orglett.5b01779
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H19 N O3 S'
_chemical_formula_sum            'C13 H19 N O3 S'
_chemical_formula_weight         269.35
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.789(2)
_cell_length_b                   11.669(3)
_cell_length_c                   15.029(4)
_cell_measurement_reflns_used    4574
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4784
_cell_measurement_theta_min      1.3550
_cell_volume                     1366.0(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  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.987
_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      0.0265
_diffrn_orient_matrix_UB_12      -0.0308
_diffrn_orient_matrix_UB_13      0.1218
_diffrn_orient_matrix_UB_21      0.0234
_diffrn_orient_matrix_UB_22      -0.0786
_diffrn_orient_matrix_UB_23      -0.0250
_diffrn_orient_matrix_UB_31      0.0625
_diffrn_orient_matrix_UB_32      0.0213
_diffrn_orient_matrix_UB_33      -0.0082
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14799
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.463
_diffrn_reflns_theta_min         2.945
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.237
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9068
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.231
_exptl_crystal_size_min          0.214
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1248 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.10(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.187
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     169
_refine_ls_number_reflns         3080
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.187
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0317P)^2^+0.3691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                3061
_reflns_number_total             3080
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01779_si_004.cif
_cod_data_source_block           sa3804
_cod_original_cell_volume        1366.0(7)
_cod_database_code               1555126
_shelxl_version_number           2013-4
_diffrn_number_total             1806
_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(H1A), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              73058
_shelx_hkl_checksum              77943