Selective demethylation of <i>O</i>-aryl glycosides by iridium-catalyzed hydrosilylation.
Jones, Caleb A. H.; Schley, Nathan D.; Chemical communications (Cambridge, England) 57 (2021) 5953–5956; doi:10.1039/d1cc00496d

data_7128329
_publ_section_title
;
 Selective demethylation of <i>O</i>-aryl glycosides by iridium-catalyzed
 hydrosilylation.
;
_journal_issue                   48
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              5953
_journal_page_last               5956
_journal_paper_doi               10.1039/d1cc00496d
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H44 O6 Si'
_chemical_formula_sum            'C25 H44 O6 Si'
_chemical_formula_weight         468.69
_chemical_name_systematic
(2?-methylphenyl)-6-O-triisopropylsilyl-2,3,4-tri-O-methyl-\a-D-mannopyranoside
_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             2020-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-28 deposited with the CCDC.	2021-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.463(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.7564(2)
_cell_length_b                   13.7188(4)
_cell_length_c                   25.4041(8)
_cell_measurement_reflns_used    15510
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.9350
_cell_measurement_theta_min      3.6130
_cell_volume                     2680.31(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.939
_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   -103.00 -43.00   1.00    1.00    --  -38.88 -57.00-150.00   60
  2  \w   -102.00 -51.00   1.00    1.00    --  -38.88 -57.00  30.00   51
  3  \w    -42.00 -15.00   1.00    1.00    --  -38.88  38.00-150.00   27
  4  \w    -88.00 -63.00   1.00    1.00    --  -38.88 -57.00 -90.00   25
  5  \w    -26.00   2.00   1.00    1.00    --   38.88 -57.00  30.00   28
  6  \w     -7.00  20.00   1.00    1.00    --   38.88 -57.00   0.00   27
  7  \w     24.00  51.00   1.00    1.00    --   38.88-125.00 -60.00   27
  8  \w     64.00  90.00   1.00    1.00    --   38.88  77.00 -60.00   26
  9  \w     51.00  78.00   1.00    1.00    --   38.88  38.00  30.00   27
 10  \w    -10.00  17.00   1.00    1.00    --   38.88 -38.00-180.00   27
 11  \w    -28.00  18.00   1.00    1.00    --   38.88 -77.00 120.00   46
 12  \w      6.00  31.00   1.00    1.00    --   38.88  88.00 -41.51   25
 13  \w     -5.00  22.00   1.00    1.00    --   38.88 -57.00 -90.00   27
 14  \w     25.00  50.00   1.00    1.00    --   38.88-125.00  90.00   25
 15  \w     14.00  71.00   1.00    1.00    --   38.88 -99.00 120.00   57
 16  \w     84.00 109.00   1.00    1.00    --   38.88  19.00 -30.00   25
 17  \w     33.00  59.00   1.00    1.00    --   38.88 -19.00 120.00   26
 18  \w     11.00  49.00   1.00    1.00    --   38.88  19.00  30.00   38
 19  \w    -14.00  27.00   1.00    1.00    --   38.88 -38.00 -60.00   41
 20  \w     13.00  40.00   1.00    1.00    --   38.88 -77.00 150.00   27
 21  \w     22.00  53.00   1.00    1.00    --   38.88 -57.00  90.00   31
 22  \w    -10.00  17.00   1.00    1.00    --   38.88 -38.00 -90.00   27
 23  \w     62.00 102.00   1.00    1.00    --   38.88  19.00 120.00   40
 24  \w     51.00  77.00   1.00    1.00    --   38.88 -99.00   0.00   26
 25  \w     41.00  87.00   1.00    1.00    --   38.88-125.00 -30.00   46
 26  \w     30.00  78.00   1.00    1.00    --   38.88 -99.00 -90.00   48
 27  \w     50.00  77.00   1.00    1.00    --   38.88  38.00-180.00   27
 28  \w     10.00  52.00   1.00    1.00    --   38.88  19.00 120.00   42
 29  \w     33.00  62.00   1.00    1.00    --   38.88 -99.00 -30.00   29
 30  \w    -29.00  67.00   1.00    1.00    --   38.88 -19.00-150.00   96
 31  \w     45.00  72.00   1.00    1.00    --   38.88  19.00 -60.00   27
 32  \w     24.00  49.00   1.00    1.00    --   38.88  38.00 -90.00   25
 33  \w      1.00  28.00   1.00    1.00    --   38.88 -77.00-120.00   27
 34  \w     60.00  98.00   1.00    1.00    --   38.88  77.00-180.00   38
 35  \w    -21.00   6.00   1.00    1.00    --   38.88 -38.00-120.00   27
 36  \w     24.00  69.00   1.00    1.00    --   38.88  77.00  60.00   45
 37  \w     -6.00  25.00   1.00    1.00    --   38.88  12.00-121.40   31
 38  \w     33.00  62.00   1.00    1.00    --   38.88  57.00-120.00   29
 39  \w     24.00  51.00   1.00    1.00    --   38.88  57.00 -90.00   27
 40  \w     79.00 106.00   1.00    1.00    --   38.88  57.00 -90.00   27
 41  \w    -27.00   4.00   1.00    1.00    --   38.88 -57.00  90.00   31
 42  \w     71.00 101.00   1.00    1.00    --   38.88  19.00-150.00   30
 43  \w     54.00  81.00   1.00    1.00    --   38.88  38.00  60.00   27
 44  \w     82.00 108.00   1.00    1.00    --   38.88  38.00  60.00   26
 45  \w     43.00 106.00   1.00    1.00    --   38.88  57.00 -30.00   63
 46  \w     13.00  51.00   1.00    1.00    --   38.88  77.00-180.00   38
 47  \w      9.00  38.00   1.00    1.00    --   38.88 -77.00-150.00   29
 48  \w     40.00  92.00   1.00    1.00    --   38.88-125.00  60.00   52
 49  \w     59.00  84.00   1.00    1.00    --   38.88-125.00-120.00   25
 50  \w     99.00 150.00   1.00    3.00    --  111.00  45.00  90.00   51
 51  \w    103.00 174.00   1.00    3.00    --  111.00  45.00 -60.00   71
 52  \w     60.00 126.00   1.00    3.00    --  111.00 -30.00-150.00   66
 53  \w    134.00 161.00   1.00    3.00    --  111.00  77.00 -90.00   27
 54  \w    104.00 149.00   1.00    3.00    --  111.00 111.00   0.00   45
 55  \w     85.00 111.00   1.00    3.00    --  111.00  77.00 -90.00   26
 56  \w     94.00 121.00   1.00    3.00    --  111.00  30.00  90.00   27
 57  \w    102.00 131.00   1.00    3.00    --  111.00 -77.00 150.00   29
 58  \w     49.00  76.00   1.00    3.00    --  111.00 -77.00 150.00   27
 59  \w     49.00  79.00   1.00    3.00    --  111.00 -94.00 -60.00   30
 60  \w     71.00 116.00   1.00    3.00    --  111.00-111.00 -30.00   45
 61  \w     45.00 129.00   1.00    3.00    --  111.00 -77.00 -30.00   84
 62  \w     55.00  82.00   1.00    3.00    --  111.00 -61.00 -60.00   27
 63  \w     59.00 132.00   1.00    3.00    --  111.00 178.00 -60.00   73
 64  \w     85.00 130.00   1.00    3.00    --  111.00 -34.00 -23.78   45
 65  \w     93.00 127.00   1.00    3.00    --  111.00  61.00-150.00   34
 66  \w    106.00 141.00   1.00    3.00    --  111.00  45.00 120.00   35
 67  \w     95.00 155.00   1.00    3.00    --  111.00  45.00-180.00   60
 68  \w     56.00 112.00   1.00    3.00    --  111.00-111.00 120.00   56
 69  \w     99.00 138.00   1.00    3.00    --  111.00  61.00   0.00   39
 70  \w     65.00 118.00   1.00    3.00    --  111.00 -45.00 -90.00   53
 71  \w     84.00 176.00   1.00    3.00    --  111.00  77.00  30.00   92
 72  \w    105.00 132.00   1.00    3.00    --  111.00 -30.00 150.00   27
 73  \w     65.00  92.00   1.00    3.00    --  111.00 -45.00  30.00   27
 74  \w     51.00 111.00   1.00    3.00    --  111.00-111.00-120.00   60
 75  \w    119.00 176.00   1.00    3.00    --  111.00 111.00 -90.00   57
 76  \w     54.00 127.00   1.00    3.00    --  111.00 -55.00-143.85   73
;
_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      -0.0774120000
_diffrn_orient_matrix_UB_12      0.0038814000
_diffrn_orient_matrix_UB_13      0.0528209000
_diffrn_orient_matrix_UB_21      -0.0667606000
_diffrn_orient_matrix_UB_22      -0.1052187000
_diffrn_orient_matrix_UB_23      -0.0089907000
_diffrn_orient_matrix_UB_31      0.1722764000
_diffrn_orient_matrix_UB_32      -0.0389785000
_diffrn_orient_matrix_UB_33      0.0295179000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.958
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            25888
_diffrn_reflns_point_group_measured_fraction_full 0.937
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.545
_diffrn_reflns_theta_min         3.509
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.055
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
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    1.161
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_exptl_crystal_size_max          0.282
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.223
_refine_diff_density_max         1.092
_refine_diff_density_min         -0.521
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 4028 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         9802
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0491P)^2^+5.9903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1505
_refine_ls_wR_factor_ref         0.1523
_reflns_Friedel_coverage         0.849
_reflns_Friedel_fraction_full    0.914
_reflns_Friedel_fraction_max     0.870
_reflns_number_gt                9346
_reflns_number_total             9802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00496d3.cif
_cod_data_source_block           3a
_cod_depositor_comments
'Adding full bibliography for 7128327--7128332.cif.'
_cod_original_cell_volume        2680.33(14)
_cod_database_code               7128329
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C25H44O6Si
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C17(H17), C20(H20), C23(H23),
 C1A(H1A), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C17A(H17A), C20A(H20A),
 C23A(H23A)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C6A(H6AA,H6AB)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C9A(H9A), C10A(H10A), C11A(H11A),
 C12A(H12A)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C13A(H13D,H13E,H13F),
 C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C18A(H18D,
 H18E,H18F), C19A(H19D,H19E,H19F), C21A(H21D,H21E,H21F), C22A(H22D,H22E,H22F),
 C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              68838
_shelx_hkl_checksum              11147
_olex2_date_sample_data_collection 2019-11-15
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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 1.162
_oxdiff_exptl_absorpt_empirical_full_min 0.827