Catalyst-Controlled Regiodivergent Synthesis of 1- and 3-Thiosugars with High Stereoselectivity and Chemoselectivity
Liu, Yuexin; Jiao, Yang; Luo, Huajun; Huang, Nianyu; Lai, Mengnan; Zou, Kun; Yao, Hui; ACS Catalysis  (2021) 5287–5293; doi:10.1021/acscatal.1c00225

data_4518611
_publ_section_title
;
 Catalyst-Controlled Regiodivergent Synthesis of 1- and 3-Thiosugars with
 High Stereoselectivity and Chemoselectivity
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5287
_journal_page_last               5293
_journal_paper_doi               10.1021/acscatal.1c00225
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H18 O4 S'
_chemical_formula_sum            'C18 H18 O4 S'
_chemical_formula_weight         330.38
_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     dual
_audit_creation_date             2020-07-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.16 svn.r6f6c53a7 for OlexSys, GUI svn.r6139)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.284(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.2212(4)
_cell_length_b                   5.7554(2)
_cell_length_c                   12.4922(5)
_cell_measurement_reflns_used    6875
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      73.2550
_cell_measurement_theta_min      3.8800
_cell_volume                     794.50(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00 -30.00  100
  2  \w   -115.00 -16.00   1.00    1.00    --  -40.98 -38.00   0.00   99
  3  \w   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00  30.00  100
  4  \w    -47.00 129.00   1.00    1.00    --   40.98   0.00 -30.00  176
  5  \w     23.00  97.00   1.00    1.00    --   40.98-125.00 150.00   74
  6  \w     74.00 178.00   1.00    1.00    --  106.95  77.00  30.00  104
  7  \w     34.00 121.00   1.00    1.00    --  106.95-125.00-180.00   87
  8  \w     25.00 109.00   1.00    1.00    --  106.95 -95.00-180.00   84
  9  \w     74.00 178.00   1.00    1.00    --  106.95  77.00   0.00  104
 10  \w     74.00 178.00   1.00    1.00    --  106.95  77.00  60.00  104
 11  \w     81.00 178.00   1.00    1.00    --  106.95  45.00  30.00   97
 12  \w     78.00 178.00   1.00    1.00    --  106.95  61.00  90.00  100
 13  \w     78.00 178.00   1.00    1.00    --  106.95  61.00   0.00  100
 14  \w     94.00 178.00   1.00    1.00    --  106.95 125.00-180.00   84
 15  \w     74.00 178.00   1.00    3.00    --  106.95  77.00 -30.00  104
 16  \w     78.00 178.00   1.00    3.00    --  106.95  61.00 -30.00  100
 17  \w     78.00 178.00   1.00    3.00    --  106.95  61.00  60.00  100
 18  \w     74.00 178.00   1.00    3.00    --  106.95  77.00 -60.00  104
 19  \w     81.00 157.00   1.00    3.00    --  106.95  45.00   0.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1316438000
_diffrn_orient_matrix_UB_12      0.0813989000
_diffrn_orient_matrix_UB_13      0.0393579000
_diffrn_orient_matrix_UB_21      -0.0260411000
_diffrn_orient_matrix_UB_22      0.0469255000
_diffrn_orient_matrix_UB_23      -0.1299470000
_diffrn_orient_matrix_UB_31      -0.0379677000
_diffrn_orient_matrix_UB_32      0.2508765000
_diffrn_orient_matrix_UB_33      0.0115290000
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8960
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.433
_diffrn_reflns_theta_min         3.913
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.968
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73124
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_description       needle
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 1113 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2938
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0530
_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^)+(0.1228P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1503
_reflns_Friedel_coverage         0.687
_reflns_Friedel_fraction_full    0.870
_reflns_Friedel_fraction_max     0.838
_reflns_number_gt                2864
_reflns_number_total             2938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00225_si_002.cif
_cod_data_source_block           lyx-59
_cod_original_cell_volume        794.51(5)
_cod_database_code               4518611
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_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:
 C11(H11), C14(H14), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              23058
_shelx_hkl_checksum              68108
_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 1.389
_oxdiff_exptl_absorpt_empirical_full_min 0.598