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_1555130
_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         'C20 H24 Br N O4 S'
_chemical_formula_sum            'C20 H24 Br N O4 S'
_chemical_formula_weight         454.37
_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'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.19 svn.r3143 for OlexSys, GUI svn.r4992)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.87(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.656(3)
_cell_length_b                   10.051(2)
_cell_length_c                   14.998(3)
_cell_measurement_reflns_used    6926
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4802
_cell_measurement_theta_min      1.4375
_cell_volume                     2135.3(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., 2013)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2013)'
_computing_structure_refinement  'ShelXL (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 0.997
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 5.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 45.1072
	          2theta: -19.7703
scan:
	Number of images: 330
	           Slice: -110.0000 - 55.0000
	     Image width: 0.5000
	        Exp time: 5.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 45.1072
	          2theta: -19.7703
scan:
	Number of images: 328
	           Slice: -110.0000 - 54.0000
	     Image width: 0.5000
	        Exp time: 5.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 180.0000
	             XTD: 45.1072
	          2theta: -19.7703
;
_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      0.0704
_diffrn_orient_matrix_UB_12      -0.0034
_diffrn_orient_matrix_UB_13      0.0045
_diffrn_orient_matrix_UB_21      0.0049
_diffrn_orient_matrix_UB_22      0.0994
_diffrn_orient_matrix_UB_23      -0.0016
_diffrn_orient_matrix_UB_31      0.0135
_diffrn_orient_matrix_UB_32      0.0005
_diffrn_orient_matrix_UB_33      0.0677
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0634
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23277
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         1.405
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.047
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.3253
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_description       Plate
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.617
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.012(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         8785
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0597
_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^)+(0.0433P)^2^+1.4854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1270
_refine_ls_wR_factor_ref         0.1338
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7546
_reflns_number_total             8785
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01779_si_005.cif
_cod_data_source_block           sa3896
_cod_database_code               1555130
_shelxl_version_number           2013-4
_diffrn_number_total             5131
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.988(12) 0.012(12)
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
3.a Riding coordinates:
 N1(H1), N2(H2A)
3.b Ternary CH refined with riding coordinates:
 C10(H10), C30(H30)
3.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C28(H28A,H28B),
 C29(H29A,H29B), C31(H31A,H31B), C32(H32A,H32B)
3.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C15(H15), C16(H16), C18(H18), C19(H19),
 C22(H22), C23(H23), C25(H25), C26(H26), C35(H35), C36(H36), C38(H38), C39(H39)
3.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C33(H33A,H33B,H33C), C40(H40A,H40B,
 H40C)
;
_shelx_res_checksum              79792
_shelx_hkl_checksum              13918
_olex2_submission_special_instructions 'No special instructions were received'