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_1555134
_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 H23 Br Cl N O4 S'
_chemical_formula_sum            'C20 H23 Br Cl N O4 S'
_chemical_formula_weight         488.81
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6751(15)
_cell_length_b                   12.590(3)
_cell_length_c                   22.275(5)
_cell_measurement_reflns_used    6778
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4817
_cell_measurement_theta_min      1.6175
_cell_volume                     2152.4(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      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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: 0.0000
	             XTD: 45.1142
	          2theta: -19.8528
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: 180.0000
	             XTD: 45.1142
	          2theta: -19.8528
;
_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      0.0443
_diffrn_orient_matrix_UB_12      0.0163
_diffrn_orient_matrix_UB_13      0.1214
_diffrn_orient_matrix_UB_21      -0.0525
_diffrn_orient_matrix_UB_22      -0.0535
_diffrn_orient_matrix_UB_23      0.0263
_diffrn_orient_matrix_UB_31      0.0301
_diffrn_orient_matrix_UB_32      -0.0327
_diffrn_orient_matrix_UB_33      -0.0066
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            16033
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.461
_diffrn_reflns_theta_min         2.442
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.156
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.265
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 1749 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         4886
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.118
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0340
_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^)+(0.0206P)^2^+0.6426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0661
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                4665
_reflns_number_total             4886
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01779_si_006.cif
_cod_data_source_block           sa3984
_cod_original_cell_volume        2152.4(7)
_cod_database_code               1555134
_diffrn_number_total             2821
_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. Rigid bond restraints
 C17, C18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
O4 \\sim O4A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(O4A)=1-FVAR(1)
 Sof(O4)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C12(H12A,H12B), C13(H13A,H13B)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18), C19(H19)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              93874
_shelx_hkl_checksum              71807
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'