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_7128332
_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         'C18 H28 O5'
_chemical_formula_sum            'C18 H28 O5'
_chemical_formula_weight         324.40
_chemical_name_systematic
'S-5 (2?-isopropylphenyl)-2,3,4-tri-O-methyl-\a-L-rhamnopyranoside'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-15
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.72846(11)
_cell_length_b                   13.3986(2)
_cell_length_c                   17.3987(3)
_cell_measurement_reflns_used    9748
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      73.2130
_cell_measurement_theta_min      4.1400
_cell_volume                     1801.64(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00 120.00   84
  2  \w   -106.00 -18.00   1.00    1.00    --  -37.09 -38.00-150.00   88
  3  \w   -104.00 -20.00   1.00    1.00    --  -37.09 -57.00 -60.00   84
  4  \w    -54.00  30.00   1.00    1.00    --  -37.09  57.00 -90.00   84
  5  \w     23.00  90.00   1.00    1.00    --   37.09-125.00-120.00   67
  6  \w     20.00 104.00   1.00    1.00    --   37.09  57.00 120.00   84
  7  \w     43.00 128.00   1.00    2.05    --  111.00 -45.00   0.00   85
  8  \w    100.00 178.00   1.00    2.05    --  111.00 111.00 -60.00   78
  9  \w     94.00 178.00   1.00    2.05    --  111.00  45.00  30.00   84
 10  \w     44.00 129.00   1.00    2.05    --  111.00 -61.00-180.00   85
 11  \w     93.00 178.00   1.00    2.05    --  111.00  61.00 -30.00   85
 12  \w     41.00 116.00   1.00    2.05    --  111.00-111.00 -30.00   75
 13  \w     57.00 150.00   1.00    2.05    --  111.00 178.00 120.00   93
 14  \w     43.00 138.00   1.00    2.05    --  111.00 -77.00   0.00   95
 15  \w    -54.00  30.00   1.00    1.00    --  -37.09  57.00  30.00   84
 16  \w    -90.00  -2.00   1.00    1.00    --  -37.09 125.00  60.00   88
 17  \w   -105.00 -10.00   1.00    1.00    --  -37.09 -77.00-150.00   95
 18  \w   -106.00 -18.00   1.00    1.00    --  -37.09 -38.00   0.00   88
 19  \w     73.00 135.00   1.00    2.05    --  111.00  15.00 -90.00   62
 20  \w     73.00 178.00   1.00    2.05    --  111.00  15.00 150.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1741465000
_diffrn_orient_matrix_UB_12      0.0025539000
_diffrn_orient_matrix_UB_13      0.0430487000
_diffrn_orient_matrix_UB_21      0.0906314000
_diffrn_orient_matrix_UB_22      -0.0366371000
_diffrn_orient_matrix_UB_23      0.0736591000
_diffrn_orient_matrix_UB_31      0.0344614000
_diffrn_orient_matrix_UB_32      0.1089350000
_diffrn_orient_matrix_UB_33      0.0237774000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0259
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            13995
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.340
_diffrn_reflns_theta_min         4.165
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.701
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.666
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.196
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.345
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1390 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     225
_refine_ls_number_reflns         3583
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0499P)^2^+0.5386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1025
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                3437
_reflns_number_total             3583
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00496d3.cif
_cod_data_source_block           2b
_cod_depositor_comments
'Adding full bibliography for 7128327--7128332.cif.'
_cod_database_code               7128332
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C18H28O5
_reflns_odcompleteness_completeness 100.00
_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. Uiso/Uaniso restraints and constraints
C15 \\sim C15A: within 3A with sigma of 0.01 and sigma for terminal atoms of
0.02
3. Others
 Sof(H13A)=Sof(C15A)=Sof(H15F)=Sof(H15D)=Sof(H15E)=1-FVAR(1)
 Sof(H13)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C13(H13A)
4.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
4.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C15A(H15F,H15D,H15E)
;
_shelx_res_checksum              80065
_shelx_hkl_checksum              11797
_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 1.389
_oxdiff_exptl_absorpt_empirical_full_min 0.763