New Class of Anion-Accelerated Amino-Cope Rearrangements as Gateway to Diverse Chiral Structures.
Chogii, Isaac; Das, Pradipta; Fell, Jason S.; Scott, Kevin A.; Crawford, Mark N.; Houk, K. N.; Njardarson, Jon T.; Journal of the American Chemical Society 139 (2017) 13141–13146; doi:10.1021/jacs.7b07319

data_4131596
_publ_section_title
;
 New Class of Anion-Accelerated Amino-Cope Rearrangements as Gateway to
 Diverse Chiral Structures.
;
_journal_issue                   37
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13141
_journal_page_last               13146
_journal_paper_doi               10.1021/jacs.7b07319
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H24 Br N O S'
_chemical_formula_sum            'C17 H24 Br N O S'
_chemical_formula_weight         370.34
_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             2017-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7214(3)
_cell_length_b                   9.7243(6)
_cell_length_c                   31.378(2)
_cell_measurement_reflns_used    3531
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      24.451
_cell_measurement_theta_min      2.596
_cell_volume                     1745.77(18)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            12358
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.677
_diffrn_reflns_theta_min         2.193
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.473
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5811
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0852 before and 0.0715 after correction.
The Ratio of minimum to maximum transmission is 0.7797.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       plate
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.4005
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.964
_refine_diff_density_min         -1.025
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.06(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         3290
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.147
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0500
_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^)+6.0259P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1137
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3017
_reflns_number_total             3290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07319_si_003.cif
_cod_data_source_block           mo_pdiv2411_0m
_cod_original_cell_volume        1745.79(18)
_cod_database_code               4131596
_shelxl_version_number           2012-9
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.94(2)
 0.06(2)
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 Ternary CH refined with riding coordinates:
 C1(H1A), C6(H6)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C2(H2A,H2B), C5(H5A,H5B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C3(H3), C13(H13), C10(H10), C4(H4), C9(H9)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_olex2_submission_special_instructions 'No special instructions were received'