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_4131597
_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         'C23 H25 N O2 S'
_chemical_formula_sum            'C23 H25 N O2 S'
_chemical_formula_weight         379.50
_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   geom
_audit_creation_date             2016-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.6544(2)
_cell_length_b                   10.1560(5)
_cell_length_c                   34.5988(15)
_cell_measurement_reflns_used    5550
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.79
_cell_measurement_theta_min      2.33
_cell_volume                     1986.87(15)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.02
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            19935
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.379
_diffrn_reflns_theta_min         2.090
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.181
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6279
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0663 before and 0.0493 after correction.
The Ratio of minimum to maximum transmission is 0.8424.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       cube
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.6
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1431 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.772
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     247
_refine_ls_number_reflns         4048
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.772
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0324
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.0986
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3690
_reflns_number_total             4048
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07319_si_002.cif
_cod_data_source_block           mo_chiii255_0m
_cod_database_code               4131597
_shelx_estimated_absorpt_t_max   0.899
_shelx_estimated_absorpt_t_min   0.899
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C1(H1A), C19(H19), C15(H15), C11(H11), C4(H4), C18(H18),
 C8(H8), C9(H9), C16(H16), C10(H10), C17(H17)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'