Metal-Free Oxidative Thioesterification of Methyl Ketones with Thiols/Disulfides for the Synthesis of α-Ketothioesters.
Hu, Biao; Zhou, Pan; Zhang, Qiaohe; Wang, Yanqin; Zhao, Siyun; Lu, Lingling; Yan, Shengjiao; Yu, Fuchao; The Journal of organic chemistry 83 (2018) 14978–14986; doi:10.1021/acs.joc.8b02235

data_4034726
_publ_section_title
;
 Metal-Free Oxidative Thioesterification of Methyl Ketones with
 Thiols/Disulfides for the Synthesis of \a-Ketothioesters.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              14978
_journal_page_last               14986
_journal_paper_doi               10.1021/acs.joc.8b02235
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H9 N O2 S2'
_chemical_formula_sum            'C12 H9 N O2 S2'
_chemical_formula_weight         263.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-27
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.12.08 svn.r3473 for OlexSys, GUI svn.r5433)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.663(3)
_cell_length_b                   14.733(4)
_cell_length_c                   17.972(5)
_cell_measurement_reflns_used    3601
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.478
_cell_measurement_theta_min      2.521
_cell_volume                     2558.6(13)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0178
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            7664
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.514
_diffrn_reflns_theta_min         2.266
_exptl_absorpt_coefficient_mu    0.404
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6539
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/3 (Bruker,2014/3) was used for absorption correction. wR2(int) was 0.0866 before and 0.0341 after correction. The Ratio of minimum to maximum transmission is 0.8770. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 949 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         2920
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0561P)^2^+0.9987P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                2459
_reflns_number_total             2920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02235_si_002.cif
_cod_data_source_block           ysj77_0m
_cod_database_code               4034726
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1A-C3 = C3-N1
 1.4 with sigma of 0.02
 S2-C3 = C3-S2A
 1.7 with sigma of 0.02
3. Rigid body (RIGU) restrains
 S2, C3, S2A, N1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, N1, C3, S2A, N1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H4B)=Sof(H5B)=Sof(S2A)=Sof(N1A)=1-FVAR(1)
 Sof(S2)=Sof(N1)=Sof(H4A)=Sof(H5A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4A), C4(H4B), C5(H5A), C5(H5B), C7(H7), C8(H8), C10(H10), C11(H11)
5.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              27888
_shelx_hkl_checksum              53328
_olex2_submission_special_instructions 'No special instructions were received'