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_4518612
_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         'C14 H15 Br O4 S'
_chemical_formula_sum            'C14 H15 Br O4 S'
_chemical_formula_weight         359.23
_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             2020-08-17
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.514(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4647(9)
_cell_length_b                   5.1138(4)
_cell_length_c                   23.6809(16)
_cell_measurement_reflns_used    3760
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.6400
_cell_measurement_theta_min      3.7320
_cell_volume                     1479.09(19)
_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-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.961
_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     38.00  72.00   1.00    1.00    --   40.73 -77.00  30.00   34
  2  \w      7.00  76.00   1.00    1.00    --   40.73 -99.00 -90.00   69
  3  \w     42.00 134.00   1.00    1.00    --  108.20 -45.00-180.00   92
  4  \w     49.00 128.00   1.00    1.00    --  108.20 -45.00 -90.00   79
  5  \w     99.00 125.00   1.00    1.00    --  108.20  30.00   0.00   26
  6  \w    152.00 178.00   1.00    1.00    --  108.20  30.00   0.00   26
  7  \w    123.00 151.00   1.00    1.00    --  108.20  77.00 -90.00   28
  8  \w     94.00 175.00   1.00    1.00    --  108.20 125.00 -90.00   81
  9  \w     26.00 106.00   1.00    1.00    --  108.20 -94.00-150.00   80
 10  \w   -113.00 -59.00   1.00    1.00    --  -40.73 -57.00  60.00   54
 11  \w   -112.00 -46.00   1.00    1.00    --  -40.73 -37.00 -30.00   66
 12  \w   -113.00 -98.00   1.00    1.00    --  -40.98 -37.00   0.00   15
;
_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      -0.0579678000
_diffrn_orient_matrix_UB_12      0.0830722000
_diffrn_orient_matrix_UB_13      0.0487699000
_diffrn_orient_matrix_UB_21      -0.1056291000
_diffrn_orient_matrix_UB_22      -0.1363270000
_diffrn_orient_matrix_UB_23      -0.0311482000
_diffrn_orient_matrix_UB_31      0.0372829000
_diffrn_orient_matrix_UB_32      -0.2556604000
_diffrn_orient_matrix_UB_33      0.0325003000
_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  0.0892
_diffrn_reflns_av_unetI/netI     0.0726
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       3
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            5629
_diffrn_reflns_point_group_measured_fraction_full 0.685
_diffrn_reflns_point_group_measured_fraction_max 0.652
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.187
_diffrn_reflns_theta_min         1.904
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.207
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21920
_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    1.613
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.976
_refine_diff_density_min         -1.644
_refine_diff_density_rms         0.273
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         3932
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0834
_refine_ls_R_factor_gt           0.0799
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1800P)^2^+11.9253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2512
_refine_ls_wR_factor_ref         0.2530
_reflns_Friedel_coverage         0.214
_reflns_Friedel_fraction_full    0.289
_reflns_Friedel_fraction_max     0.260
_reflns_number_gt                3775
_reflns_number_total             3932
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00225_si_003.cif
_cod_data_source_block           lyx-72
_cod_database_code               4518612
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95(4)
 0.05(4)
2. 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
3. Uiso/Uaniso restraints and constraints
Uanis(O7) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.2
Uanis(C14) \\sim Ueq: with sigma of 0.0005 and sigma for terminal atoms of 0.001
4.a Ternary CH refined with riding coordinates:
 C24(H24), C11(H11), C10(H10), C25(H25), C21(H21), C7(H7)
4.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C12(H12A,H12B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C23(H23), C2(H2), C6(H6), C16(H16), C5(H5), C20(H20), C9(H9), C8(H8A),
  C22(H22), C19(H19), C17(H17)
4.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C14(H14A,H14B,H14C)
4.e Idealised tetrahedral OH refined as rotating group:
 O8(H8), O1(H1)
;
_shelx_res_checksum              32670
_shelx_hkl_checksum              50464
_olex2_date_sample_data_collection 2020-08-17
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.360
_oxdiff_exptl_absorpt_empirical_full_min 0.435