Synthesis of N,N-disubstituted 2-aminothiophenes by the cyclization of gem-difluoroalkenes with β-keto thioamides.
Zhang, Xuxue; Wu, Mingsheng; Zhang, Juan; Cao, Song; Organic & biomolecular chemistry 15 (2017) 2436–2442; doi:10.1039/c7ob00368d

data_7155509
_publ_section_title
;
 Synthesis of N,N-disubstituted 2-aminothiophenes by the cyclization of
 gem-difluoroalkenes with \b-keto thioamides.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2436
_journal_page_last               2442
_journal_paper_doi               10.1039/c7ob00368d
_journal_volume                  15
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C28 H25 N O S'
_chemical_formula_sum            'C28 H25 N O S'
_chemical_formula_weight         423.55
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/cc1k54tp
_audit_creation_date             2015-06-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-11-03 deposited with the CCDC.
2017-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.443(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.9949(9)
_cell_length_b                   10.2229(14)
_cell_length_c                   15.438(2)
_cell_measurement_reflns_used    3055
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      24.64
_cell_measurement_theta_min      2.39
_cell_volume                     1099.0(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0234
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9424
_diffrn_reflns_point_group_measured_fraction_full 0.880
_diffrn_reflns_point_group_measured_fraction_max 0.865
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.080
_diffrn_reflns_theta_min         1.325
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.168
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6383
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1123 before and 0.0393 after correction.
The Ratio of minimum to maximum transmission is 0.8561.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.135
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1292 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         4639
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0413P)^2^+0.0531P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0862
_reflns_Friedel_coverage         0.641
_reflns_Friedel_fraction_full    0.743
_reflns_Friedel_fraction_max     0.715
_reflns_number_gt                3804
_reflns_number_total             4639
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00368d2.cif
_cod_data_source_block           mo_dm15499_0m
_cod_depositor_comments          'Adding full bibliography for 7155509.cif.'
_cod_database_code               7155509
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.959
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C11(H11), C12(H12), C14(H14), C15(H15), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
;
_shelx_res_checksum              17410
_olex2_submission_special_instructions 'No special instructions were received'