Construction of thioglycoside bonds <i>via</i> an asymmetric organocatalyzed sulfa-Michael/aldol reaction: access to 4'-thionucleosides.
Wei, Tao; Xie, Ming-Sheng; Guo, Hai-Ming; Chemical communications (Cambridge, England) 60 (2024) 5018–5021; doi:10.1039/d4cc00984c

data_7132941
_publ_section_title
;
 Construction of thioglycoside bonds <i>via</i> an asymmetric
 organocatalyzed sulfa-Michael/aldol reaction: access to
 4'-thionucleosides.
;
_journal_issue                   38
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5018
_journal_page_last               5021
_journal_paper_doi               10.1039/d4cc00984c
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H22 N2 O2 S'
_chemical_formula_sum            'C17 H22 N2 O2 S'
_chemical_formula_weight         318.42
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-12-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-30 deposited with the CCDC.	2024-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.3770(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.90480(10)
_cell_length_b                   14.2184(2)
_cell_length_c                   11.99560(10)
_cell_measurement_reflns_used    30892
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.2550
_cell_measurement_theta_min      4.3250
_cell_volume                     1743.51(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -105.00 -16.00   1.00    1.00    --  -35.62 -34.00 165.00   89
  2  \w    -56.00  34.00   1.00    1.00    --  -35.62  34.00 -36.00   90
  3  \w     16.00 105.00   1.00    1.00    --   35.62  34.00 -36.00   89
  4  \w    -34.00  56.00   1.00    1.00    --   35.62 -34.00 165.00   90
  5  \w     87.00 177.00   1.00    1.00    --  107.12  34.00 -36.00   90
  6  \w     38.00 127.00   1.00    1.00    --  107.12 -34.00 165.00   89
  7  \w   -108.00 -34.00   1.00    1.00    --  -35.62 178.00 -30.00   74
  8  \w   -108.00 -35.00   1.00    1.00    --  -35.62-178.00  30.00   73
  9  \w     57.00 108.00   1.00    1.00    --   35.62 178.00-150.00   51
 10  \w     57.00 108.00   1.00    1.00    --   35.62 178.00 150.00   51
 11  \w      9.00 103.00   1.00    1.00    --   35.62  77.00  90.00   94
 12  \w     57.00 108.00   1.00    1.00    --   35.62 178.00  30.00   51
 13  \w      6.00 107.00   1.00    1.00    --   35.62  19.00-150.00  101
 14  \w     -1.00  26.00   1.00    1.00    --   35.62  94.00 124.09   27
 15  \w      9.00 103.00   1.00    1.00    --   35.62  77.00  60.00   94
 16  \w      6.00 107.00   1.00    1.00    --   35.62  19.00 150.00  101
 17  \w     19.00 103.00   1.00    1.00    --   35.62  57.00  30.00   84
 18  \w     19.00 103.00   1.00    1.00    --   35.62  57.00 150.00   84
 19  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  30.00   95
 20  \w     69.00 178.00   1.00    1.00    --  107.12  15.00-180.00  109
 21  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  90.00   95
 22  \w    100.00 177.00   1.00    1.00    --  107.12 111.00-180.00   77
 23  \w     80.00 175.00   1.00    1.00    --  107.12  77.00  60.00   95
 24  \w     39.00 125.00   1.00    1.00    --  107.12 -45.00  60.00   86
 25  \w     38.00 110.00   1.00    1.00    --  107.12 -95.00-120.00   72
 26  \w     90.00 176.00   1.00    1.00    --  107.12  43.00  44.66   86
 27  \w     89.00 174.00   1.00    1.00    --  107.12  61.00  60.00   85
 28  \w     89.00 174.00   1.00    1.00    --  107.12  61.00   0.00   85
 29  \w     86.00 177.00   1.00    1.00    --  107.12  30.00  90.00   91
 30  \w     38.00 110.00   1.00    1.00    --  107.12 -95.00 -60.00   72
 31  \w     90.00 176.00   1.00    1.00    --  107.12  45.00  30.00   86
 32  \w     86.00 177.00   1.00    1.00    --  107.12  30.00 120.00   91
 33  \w     89.00 174.00   1.00    1.00    --  107.12  61.00  30.00   85
 34  \w     89.00 174.00   1.00    1.00    --  107.12  61.00  90.00   85
 35  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 -30.00   95
 36  \w     89.00 174.00   1.00    1.00    --  107.12  61.00 120.00   85
 37  \w     90.00 176.00   1.00    1.00    --  107.12  45.00  90.00   86
 38  \w     86.00 177.00   1.00    1.00    --  107.12  30.00 150.00   91
 39  \w     86.00 177.00   1.00    1.00    --  107.12  30.00  60.00   91
 40  \w     86.00 177.00   1.00    1.00    --  107.12  30.00  30.00   91
 41  \w     80.00 175.00   1.00    1.00    --  107.12  77.00   0.00   95
 42  \w     90.00 176.00   1.00    1.00    --  107.12  45.00 150.00   86
 43  \w     86.00 177.00   1.00    1.00    --  107.12  30.00   0.00   91
 44  \w     69.00 178.00   1.00    1.00    --  107.12  15.00  60.00  109
 45  \w     38.00 110.00   1.00    1.00    --  107.12 -95.00 120.00   72
 46  \w   -107.00  -6.00   1.00    1.00    --  -35.62 -19.00-150.00  101
 47  \w     19.00 103.00   1.00    1.00    --   35.62  57.00   0.00   84
 48  \w      1.00  75.00   1.00    1.00    --   35.62 -99.00   0.00   74
 49  \w      1.00  28.00   1.00    1.00    --   35.62  92.00 -21.78   27
 50  \w      9.00 103.00   1.00    1.00    --   35.62  77.00-120.00   94
 51  \w     55.00 108.00   1.00    1.00    --   35.62-178.00 -60.00   53
 52  \w      9.00 103.00   1.00    1.00    --   35.62  77.00 -90.00   94
 53  \w     19.00 103.00   1.00    1.00    --   35.62  57.00-180.00   84
 54  \w      9.00 103.00   1.00    1.00    --   35.62  77.00 -60.00   94
 55  \w      1.00  75.00   1.00    1.00    --   35.62 -99.00 -90.00   74
 56  \w     19.00 103.00   1.00    1.00    --   35.62  57.00-150.00   84
 57  \w      9.00 103.00   1.00    1.00    --   35.62  77.00   0.00   94
 58  \w     55.00 108.00   1.00    1.00    --   35.62-178.00-180.00   53
 59  \w      1.00  75.00   1.00    1.00    --   35.62 -99.00-180.00   74
 60  \w     89.00 174.00   1.00    1.00    --  107.12  61.00-120.00   85
 61  \w     37.00 113.00   1.00    1.00    --  107.12-111.00-150.00   76
 62  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 -60.00   95
 63  \w     80.00 175.00   1.00    1.00    --  107.12  77.00-120.00   95
 64  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 150.00   95
 65  \w     80.00 175.00   1.00    1.00    --  107.12  77.00-180.00   95
 66  \w     37.00 113.00   1.00    1.00    --  107.12-111.00  30.00   76
 67  \w     80.00 175.00   1.00    1.00    --  107.12  77.00 -90.00   95
 68  \w     80.00 175.00   1.00    1.00    --  107.12  77.00-150.00   95
 69  \w     89.00 174.00   1.00    1.00    --  107.12  61.00 -90.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1474212000
_diffrn_orient_matrix_UB_12      0.0205850000
_diffrn_orient_matrix_UB_13      0.0354083000
_diffrn_orient_matrix_UB_21      -0.0238109000
_diffrn_orient_matrix_UB_22      0.0428776000
_diffrn_orient_matrix_UB_23      -0.1237542000
_diffrn_orient_matrix_UB_31      -0.0206914000
_diffrn_orient_matrix_UB_32      0.0973221000
_diffrn_orient_matrix_UB_33      0.0469016000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0746
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            44786
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.391
_diffrn_reflns_theta_min         3.931
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.713
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22446
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.257
_refine_diff_density_min         -0.545
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6391
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0768
_refine_ls_R_factor_gt           0.0732
_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^)+(0.1647P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2000
_refine_ls_wR_factor_ref         0.2085
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    0.886
_reflns_Friedel_fraction_max     0.877
_reflns_number_gt                5998
_reflns_number_total             6391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00984c2.cif
_cod_data_source_block           wt-20211217
_cod_depositor_comments          'Adding full bibliography for 7132941.cif.'
_cod_database_code               7132941
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'S1 N1 C1 O1'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C10(H10), C32(H32), C33(H33), C34(H34)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C3(H3), C2(H2), C25(H25), C26(H26), C27(H27), C28(H28)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C44(H44A,
 H44B,H44C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O43(H43)
;
_shelx_res_checksum              6900
_shelx_hkl_checksum              95382
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 6.697
_oxdiff_exptl_absorpt_empirical_full_min 0.472