Synthesis of glycosyl sulfoximines by a highly chemo- and stereoselective NH- and O-transfer to thioglycosides.
Tota, Arianna; Carlucci, Claudia; Pisano, Luisa; Cutolo, Giuliano; Clarkson, Guy J.; Romanazzi, Giuseppe; Degennaro, Leonardo; Bull, James A.; Rollin, Patrick; Luisi, Renzo; Organic & biomolecular chemistry 18 (2020) 3893–3897; doi:10.1039/d0ob00647e

data_7157491
_publ_section_title
;
 Synthesis of glycosyl sulfoximines by a highly chemo- and stereoselective
 NH- and O-transfer to thioglycosides.
;
_journal_issue                   20
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3893
_journal_page_last               3897
_journal_paper_doi               10.1039/d0ob00647e
_journal_volume                  18
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C20 H31 N O10 S), C5 H12'
_chemical_formula_sum            'C45 H74 N2 O20 S2'
_chemical_formula_weight         1027.18
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-01-24 deposited with the CCDC.	2020-05-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.74142(5)
_cell_length_b                   9.74142(5)
_cell_length_c                   55.7588(4)
_cell_measurement_reflns_used    25529
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.6410
_cell_measurement_theta_min      3.1180
_cell_volume                     5291.25(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6093
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -90.00  108
  2  \w    -66.00  33.00   1.00    1.00    --  -41.82  37.00-180.00   99
  3  \w    103.00 178.00   1.00    4.00    --  107.00  77.00 120.00   75
  4  \w    103.00 178.00   1.00    4.00    --  107.00  77.00  60.00   75
  5  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-150.00   97
  6  \w    103.00 178.00   1.00    4.00    --  107.00  77.00   0.00   75
  7  \w     81.00 178.00   1.00    4.00    --  107.00  45.00-120.00   97
  8  \w     81.00 178.00   1.00    4.00    --  107.00  45.00 -30.00   97
  9  \w     35.00 136.00   1.00    4.00    --  107.00 -61.00 -90.00  101
 10  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00-120.00  100
 11  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00  30.00  100
 12  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 150.00  100
 13  \w     81.00 178.00   1.00    4.00    --  107.00  45.00  90.00   97
 14  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00-150.00   83
 15  \w     34.00 112.00   1.00    4.00    --  107.00-125.00 120.00   78
 16  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 -90.00  100
 17  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 150.00  100
 18  \w     34.00 112.00   1.00    4.00    --  107.00-125.00-180.00   78
 19  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00  90.00  100
 20  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 -30.00  100
 21  \w     61.00 131.00   1.00    1.00    --   41.82 178.00 150.00   70
 22  \w     78.00 178.00   1.00    4.00    --  107.00  61.00 120.00  100
 23  \w     78.00 178.00   1.00    4.00    --  107.00  61.00   0.00  100
 24  \w     24.00 107.00   1.00    4.00    --  107.00 -94.00 -90.00   83
 25  \w     78.00 162.00   1.00    4.00    --  107.00  61.00 -60.00   84
 26  \w     78.00 178.00   1.00    4.00    --  107.00  61.00  30.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0031424000
_diffrn_orient_matrix_UB_12      0.1543298000
_diffrn_orient_matrix_UB_13      -0.0059787000
_diffrn_orient_matrix_UB_21      -0.0220009000
_diffrn_orient_matrix_UB_22      -0.0343954000
_diffrn_orient_matrix_UB_23      -0.0266963000
_diffrn_orient_matrix_UB_31      -0.1565826000
_diffrn_orient_matrix_UB_32      0.0017829000
_diffrn_orient_matrix_UB_33      0.0038777000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       68
_diffrn_reflns_limit_l_min       -69
_diffrn_reflns_number            78929
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.704
_diffrn_reflns_theta_min         3.170
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.547
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.01863
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019)
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    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             2200
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.639
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1983 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: 0.007(5) Shelx 2018
Hooft y: -0.002(5)  Olex2
the molecule contains known chiral centres that are not affected by the synthetic steps
;
_refine_ls_abs_structure_Flack   0.007(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     320
_refine_ls_number_reflns         5339
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0544P)^2^+5.3337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1189
_refine_ls_wR_factor_ref         0.1193
_reflns_Friedel_coverage         0.648
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5274
_reflns_number_total             5339
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00647e2.cif
_cod_data_source_block           rl3
_cod_depositor_comments          'Adding full bibliography for 7157491.cif.'
_cod_original_cell_volume        5291.24(7)
_cod_database_code               7157491
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.654
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
The determination of the oxygen and nitrogen of the sulfoximine was decided by taking into account the thermal 
ellipsoids of the two atoms, bond lengths (S=O shorter than S=N as confirmed from related structures in the CCDC) 
and the hydrogen was located in a difference map confirming the identity of the nitrogen (see below). 
The hydrogen (H7) on the nitrogen was located in a difference map and its position allowed to refine freely but 
given thermal ellipsoids 1.2 times the equivalent isotropic displacement parameter of N7

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 C100, C101, C102
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
3. Others
 Fixed Sof: H10G(0.5) H10F(0.5)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C13(H13A,
 H13B), C101(H10D,H10E), C102(H10G,H10F)
4.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C22(H22A,H22B,
 H22C), C100(H10A,H10B,H10C)
;
_shelx_res_checksum              97357
_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 31.292
_oxdiff_exptl_absorpt_empirical_full_min 0.497