Aminative Umpolung cyclization for synthesis of chiral exocyclic vicinal diamines.
Liu, Feng; Zhao, Guoqing; Cai, Weiqi; Xu, Dongfang; Zhao, Baoguo; Organic & biomolecular chemistry 16 (2018) 7498–7502; doi:10.1039/c8ob02000k

data_7156449
_publ_section_title
;
 Aminative Umpolung cyclization for synthesis of chiral exocyclic vicinal
 diamines.
;
_journal_issue                   40
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7498
_journal_page_last               7502
_journal_paper_doi               10.1039/c8ob02000k
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C31 H28 F2 N2 O S'
_chemical_formula_sum            'C31 H28 F2 N2 O S'
_chemical_formula_weight         514.61
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc20htn0
_audit_creation_date             2017-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2018-08-15 deposited with the CCDC.
2018-09-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0912(17)
_cell_length_b                   17.553(3)
_cell_length_c                   20.148(4)
_cell_measurement_reflns_used    3136
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      20.640
_cell_measurement_theta_min      2.331
_cell_volume                     3215.2(10)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296
_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_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0773
_diffrn_reflns_av_unetI/netI     0.0804
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25952
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.518
_diffrn_reflns_theta_min         2.022
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.134
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6151
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0621 before and 0.0516 after correction. The Ratio of minimum to maximum transmission is 0.8250. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.063
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.437
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 1132 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         7376
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1577
_refine_ls_R_factor_gt           0.0670
_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^)+(0.1173P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1780
_refine_ls_wR_factor_ref         0.2264
_reflns_Friedel_coverage         0.784
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3365
_reflns_number_total             7376
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob02000k2.cif
_cod_data_source_block           mo_dm17172_0m
_cod_depositor_comments
'Adding full bibliography for 7156449--7156450.cif.'
_cod_original_cell_volume        3215.1(10)
_cod_database_code               7156449
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.974
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C26) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
3.a Ternary CH refined with riding coordinates:
 C1(H1), C14(H14)
3.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C4(H4), C6(H6), C9(H9), C11(H11), C12(H12), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C30(H30),
  C31(H31)
3.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              81298
_shelx_fab_checksum              69378
_olex2_submission_special_instructions 'No special instructions were received'