Selective synthesis of aryl thioamides and aryl-α-ketoamides from α-oxocarboxylic acids and tetraalkylthiuram disulfides: an unexpected chemoselectivity from aryl sulfonyl chlorides
Lai, Miao; Wu, Zhiyong; Wang, Yizhi; Zheng, Ying; Zhao, Mingqin; Organic Chemistry Frontiers 6 (2019) 506–; doi:10.1039/C8QO01127C

data_1554512
_publ_section_title
;
 Selective synthesis of aryl thioamides and aryl-\a-ketoamides from
 \a-oxocarboxylic acids and tetraalkylthiuram disulfides: an unexpected
 chemoselectivity from aryl sulfonyl chlorides
;
_journal_issue                   4
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              506
_journal_paper_doi               10.1039/C8QO01127C
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety         'C12 H17 N S'
_chemical_formula_sum            'C12 H17 N S'
_chemical_formula_weight         207.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-09-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-10-18 deposited with the CCDC.
2018-12-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.051(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.3585(5)
_cell_length_b                   10.9450(11)
_cell_length_c                   17.5672(13)
_cell_measurement_reflns_used    1344
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.4750
_cell_measurement_theta_min      4.7510
_cell_volume                     1221.78(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -104.00  -11.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -37.0000   30.0000 93

  2 omega  -11.00   15.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000    0.0000  120.0000 26

  3 omega  -93.00  -38.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000    0.0000  120.0000 55

  4 omega   64.00  100.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   60.0000 36

  5 omega   64.00   94.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   90.0000 30

  6 omega   68.00   98.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -30.0000 30

  7 omega   59.00  108.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000 -120.0000 49

  8 omega   12.00   38.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000 -120.0000 26

  9 omega   63.00  109.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -90.0000 46

 10 omega   41.00   81.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 40

 11 omega  150.00  176.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   90.0000 26

 12 omega   96.00  178.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   30.0000 82

 13 omega   92.00  176.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   90.0000 84

 14 omega  103.00  128.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   90.0000 25

 15 omega  105.00  135.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 30

 16 omega   45.00   98.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 53

 17 omega   41.00   99.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 58

 18 omega   72.00   97.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 25

 19 omega   39.00   68.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 29

 20 omega   39.00   90.00   1.0000   44.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0923967000
_diffrn_orient_matrix_UB_12      0.0934857000
_diffrn_orient_matrix_UB_13      0.0576134000
_diffrn_orient_matrix_UB_21      -0.0728210000
_diffrn_orient_matrix_UB_22      -0.0800727000
_diffrn_orient_matrix_UB_23      0.0661812000
_diffrn_orient_matrix_UB_31      0.2119314000
_diffrn_orient_matrix_UB_32      -0.0683112000
_diffrn_orient_matrix_UB_33      0.0011278000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_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            4465
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.026
_diffrn_reflns_theta_max         67.026
_diffrn_reflns_theta_min         4.761
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.041
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86759
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.127
_exptl_crystal_description       prism
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.259
_refine_diff_density_rms         0.052
_refine_ls_extinction_coef       0.0065(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     144
_refine_ls_number_reflns         2177
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0566
_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^)+(0.0886P)^2^+0.1650P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1577
_refine_ls_wR_factor_ref         0.1751
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1559
_reflns_number_total             2177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo01127c2.cif
_cod_data_source_block           201809391
_cod_database_code               1554512
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2S1
_shelx_estimated_absorpt_t_max   0.887
_shelx_estimated_absorpt_t_min   0.723
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C5, C6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
Uanis(C8) = Uanis(C8A)
4. Others
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=FVAR(1)
5.a Riding coordinates:
 C8(H8), C8A(H8A)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C10(H10A,H10B,H10C), C10A(H10D,H10E,
 H10F), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'