Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions: Applications to Gluco- and Mannopyranosyl Sulfoxide and Trichloroacetimidate Type Donors.
Adero, Philip O.; Furukawa, Takayuki; Huang, Min; Mukherjee, Debaraj; Retailleau, Pascal; Bohé, Luis; Crich, David; Journal of the American Chemical Society 137 (2015) 10336–10345; doi:10.1021/jacs.5b06126

data_4124255
_publ_section_title
;
 Cation Clock Reactions for the Determination of Relative Reaction
 Kinetics in Glycosylation Reactions: Applications to Gluco- and
 Mannopyranosyl Sulfoxide and Trichloroacetimidate Type Donors.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10336
_journal_page_last               10345
_journal_paper_doi               10.1021/jacs.5b06126
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H26 O5'
_chemical_formula_sum            'C24 H26 O5'
_chemical_formula_weight         394.45
_chemical_name_systematic
; 
 (2R,4aR,9aS,10R,10aR)-10-(benzyloxy)-7-methylene-2-
phenyloctahydro-4H-pyrano[2',3':5,6]pyrano[3,2-d][1,3]dioxine
;
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                104.163(7)
_cell_angle_beta                 100.372(7)
_cell_angle_gamma                103.601(8)
_cell_formula_units_Z            4
_cell_length_a                   11.3740(6)
_cell_length_b                   12.3617(6)
_cell_length_c                   15.9539(11)
_cell_measurement_reflns_used    6104
_cell_measurement_temperature    203(2)
_cell_measurement_theta_max      68.3
_cell_measurement_theta_min      3.0
_cell_volume                     2045.7(2)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)'
_computing_molecular_graphics    'PLATON (Spek, 2009)'
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      203(2)
_diffrn_detector_type
'RAPID II large area curved imaging plate detector '
_diffrn_measured_fraction_theta_full 0.960
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_details
;
scan:
    Number of images: 36
               Slice: 20.0000 - 200.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 90.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 36
               Slice: 20.0000 - 200.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 50.0000
                 Phi: 270.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 31
               Slice: 20.0000 - 176.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 50.0000
                 Phi: 180.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 21
               Slice: 20.0000 - 128.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 50.0000
                 Phi: 0.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 18
               Slice: 20.0000 - 110.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 30.0000
                 Phi: 270.0000
                 XTD: 127.4000
              2theta: 0.0000
scan:
    Number of images: 12
               Slice: 35.0000 - 95.0000
         Image width: 5.0000
            Exp time: 150.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 50.0000
                 Phi: 90.0000
                 XTD: 127.4000
              2theta: 0.0000

;
_diffrn_measurement_device_type  'Rigaku rapid II RAXIS conversion'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      -0.060067
_diffrn_orient_matrix_UB_12      -0.063917
_diffrn_orient_matrix_UB_13      -0.051966
_diffrn_orient_matrix_UB_21      -0.017122
_diffrn_orient_matrix_UB_22      -0.049366
_diffrn_orient_matrix_UB_23      0.040114
_diffrn_orient_matrix_UB_31      -0.069545
_diffrn_orient_matrix_UB_32      0.033027
_diffrn_orient_matrix_UB_33      0.012371
_diffrn_radiation_monochromator  'Osmic CMF mirrors'
_diffrn_radiation_source         'rotating anode mm007HF'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0480
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.960
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20758
_diffrn_reflns_point_group_measured_fraction_full 0.696
_diffrn_reflns_point_group_measured_fraction_max 0.692
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.238
_diffrn_reflns_theta_min         2.952
_exptl_absorpt_coefficient_mu    0.722
_exptl_absorpt_correction_T_max  0.84
_exptl_absorpt_correction_T_min  0.48
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'FS_ABSCOR (Rigaku, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_description       stick
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.59
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.280
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 2399 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.18(9)
_refine_ls_extinction_coef       0.00139(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.190
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1046
_refine_ls_number_reflns         10378
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.190
_refine_ls_R_factor_all          0.0710
_refine_ls_R_factor_gt           0.0450
_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^)+(0.0247P)^2^+1.1020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.446
_reflns_Friedel_fraction_full    0.432
_reflns_Friedel_fraction_max     0.427
_reflns_number_gt                7959
_reflns_number_total             10378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b06126_si_003.cif
_cod_data_source_block           CCDC_878445
_cod_depositor_comments
'Adding full bibliography for 4124255--4124256.cif.'
_cod_database_code               4124255
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.931
_shelx_estimated_absorpt_t_max   0.931
_shelx_res_checksum              31511
_shelx_hkl_checksum              67430