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_7128328
_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         'C15 H20 Cl2 O5'
_chemical_formula_sum            'C15 H20 Cl2 O5'
_chemical_formula_weight         351.21
_chemical_name_systematic
(2?,4?-dichlorophenyl)-2,3,4-tri-O-methyl-\a-L-rhamnopyranoside
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-28
_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                64.328(2)
_cell_angle_beta                 88.439(2)
_cell_angle_gamma                86.714(2)
_cell_formula_units_Z            3
_cell_length_a                   8.2374(2)
_cell_length_b                   12.4665(2)
_cell_length_c                   13.7074(3)
_cell_measurement_reflns_used    20368
_cell_measurement_temperature    99.97(10)
_cell_measurement_theta_max      71.6410
_cell_measurement_theta_min      3.5650
_cell_volume                     1266.59(5)
_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      99.97(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -34.00  -7.00   1.00    1.00    --   20.00 126.00 134.42   27
  2  \w   -108.00  -7.00   1.00    1.00    --  -36.45 -19.00 -60.00  101
  3  \w   -109.00 -39.00   1.00    1.00    --  -36.45-178.00 -90.00   70
  4  \w   -109.00 -39.00   1.00    1.00    --  -36.45-178.00 120.00   70
  5  \w    -55.00  33.00   1.00    1.00    --  -36.45  38.00 120.00   88
  6  \w   -109.00 -39.00   1.00    1.00    --  -36.45-178.00-180.00   70
  7  \w     30.00  94.00   1.00    1.00    --   36.45-132.00-164.00   64
  8  \w     18.00 106.00   1.00    1.00    --   36.45  38.00  90.00   88
  9  \w     34.00  97.00   1.00    1.00    --   36.45-137.00  18.00   63
 10  \w      4.00  30.00   1.00    1.00    --   36.45  88.00 -23.83   26
 11  \w      4.00  30.00   1.00    1.00    --   36.45  88.00-130.28   26
 12  \w      2.00  29.00   1.00    1.00    --   36.45  90.00 155.17   27
 13  \w      2.00  29.00   1.00    1.00    --   36.45  90.00  85.72   27
 14  \w     15.00  42.00   1.00    1.00    --   44.00  81.00 -19.70   27
 15  \w     15.00  42.00   1.00    1.00    --   44.00  81.00  56.21   27
 16  \w     16.00  42.00   1.00    1.00    --   44.00  80.00 170.68   26
 17  \w     25.00 115.00   1.00    1.00    --   48.00  71.00  24.39   90
 18  \w     27.00 119.00   1.00    1.00    --   52.00  73.00 -88.07   92
 19  \w     27.00 119.00   1.00    1.00    --   52.00  74.00-135.97   92
 20  \w     28.00 119.00   1.00    1.00    --   52.00  72.00 134.12   91
 21  \w     27.00 119.00   1.00    1.00    --   52.00  74.00 166.70   92
 22  \w     31.00 123.00   1.00    1.00    --   56.00  74.00 -39.49   92
 23  \w     31.00 123.00   1.00    1.00    --   56.00  73.00  80.92   92
 24  \w     90.00 175.00   1.00    1.00    --  107.73  61.00-180.00   85
 25  \w     90.00 175.00   1.00    1.00    --  107.73  61.00 -60.00   85
 26  \w     90.00 175.00   1.00    1.00    --  107.73  61.00 120.00   85
 27  \w     90.00 175.00   1.00    1.00    --  107.73  61.00 -90.00   85
 28  \w     38.00 108.00   1.00    1.00    --  107.73-111.00 -90.00   70
 29  \w     90.00 175.00   1.00    1.00    --  107.73  61.00 -30.00   85
 30  \w     40.00 134.00   1.00    1.00    --  107.73 -77.00 -90.00   94
 31  \w     90.00 175.00   1.00    1.00    --  107.73  61.00 150.00   85
 32  \w     90.00 176.00   1.00    1.00    --  107.73  45.00 120.00   86
 33  \w     90.00 176.00   1.00    1.00    --  107.73  45.00  60.00   86
 34  \w     90.00 176.00   1.00    1.00    --  107.73  45.00 -30.00   86
 35  \w     90.00 176.00   1.00    1.00    --  107.73  45.00 -90.00   86
 36  \w     61.00 146.00   1.00    1.00    --  107.73 178.00 -60.00   85
 37  \w     38.00 107.00   1.00    1.00    --  107.73 -94.00 -30.00   69
 38  \w     90.00 176.00   1.00    1.00    --  107.73  45.00 150.00   86
 39  \w     90.00 176.00   1.00    1.00    --  107.73  45.00-180.00   86
 40  \w     90.00 176.00   1.00    1.00    --  107.73  45.00-150.00   86
 41  \w     90.00 176.00   1.00    1.00    --  107.73  45.00  30.00   86
 42  \w     90.00 176.00   1.00    1.00    --  107.73  45.00  90.00   86
 43  \w     41.00 126.00   1.00    1.00    --  107.73 -61.00  60.00   85
 44  \w     90.00 175.00   1.00    1.00    --  107.73  61.00-150.00   85
 45  \w     90.00 176.00   1.00    1.00    --  107.73  45.00 -60.00   86
 46  \w     90.00 175.00   1.00    1.00    --  107.73  61.00-120.00   85
 47  \w     90.00 176.00   1.00    1.00    --  107.73  45.00   0.00   86
 48  \w     90.00 175.00   1.00    1.00    --  107.73  61.00  90.00   85
 49  \w     90.00 175.00   1.00    1.00    --  107.73  61.00  30.00   85
 50  \w     90.00 176.00   1.00    1.00    --  107.73  45.00-120.00   86
 51  \w    133.00 171.00   1.00    1.00    --  107.73  61.00  60.00   38
 52  \w     48.00 108.00   1.00    1.00    --  107.73-111.00  90.00   60
 53  \w     91.00 119.00   1.00    1.00    --  107.73  61.00   0.00   28
 54  \w     90.00 118.00   1.00    1.00    --  107.73  61.00  60.00   28
;
_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      0.0275344000
_diffrn_orient_matrix_UB_12      -0.1319286000
_diffrn_orient_matrix_UB_13      0.0805770000
_diffrn_orient_matrix_UB_21      -0.0194837000
_diffrn_orient_matrix_UB_22      0.0343048000
_diffrn_orient_matrix_UB_23      0.0951401000
_diffrn_orient_matrix_UB_31      -0.1842669000
_diffrn_orient_matrix_UB_32      -0.0162896000
_diffrn_orient_matrix_UB_33      0.0023201000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0192
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            24899
_diffrn_reflns_point_group_measured_fraction_full 0.890
_diffrn_reflns_point_group_measured_fraction_max 0.871
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.758
_diffrn_reflns_theta_min         3.578
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.638
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.415
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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       block
_exptl_crystal_F_000             552
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.327
_exptl_crystal_size_mid          0.209
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 3676 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     607
_refine_ls_number_reflns         8630
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0218
_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^)+(0.0334P)^2^+0.2859P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0573
_refine_ls_wR_factor_ref         0.0574
_reflns_Friedel_coverage         0.768
_reflns_Friedel_fraction_full    0.780
_reflns_Friedel_fraction_max     0.756
_reflns_number_gt                8570
_reflns_number_total             8630
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00496d3.cif
_cod_data_source_block           2d
_cod_depositor_comments
'Adding full bibliography for 7128327--7128332.cif.'
_cod_database_code               7128328
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C15H20Cl2O5
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(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), C1C(H1C), C2C(H2C), C3C(H3C),
 C4C(H4C), C5C(H5C), C1B(H1B), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C11(H11), C12(H12), C9C(H9C), C11C(H11C), C12C(H12C), C9B(H9B),
 C11B(H11B), C12B(H12B)
2.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C6C(H6CA,H6CB,H6CC), C13C(H13D,H13E,H13F), C14C(H14D,H14E,H14F),
 C15C(H15D,H15E,H15F), C6B(H6BA,H6BB,H6BC), C13B(H13G,H13H,H13I), C14B(H14G,
 H14H,H14I), C15B(H15G,H15H,H15I)
;
_shelx_res_checksum              51866
_shelx_hkl_checksum              1599
_olex2_date_sample_data_collection 2020-03-11
_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 1.285
_oxdiff_exptl_absorpt_empirical_full_min 0.887