Are Brønsted Acids the True Promoter of Metal-Triflate-Catalyzed Glycosylations? A Mechanistic Probe into 1,2-cis-Aminoglycoside Formation by Nickel Triflate
Sletten, Eric T.; Tu, Yi-Jung; Schlegel, H. Bernhard; Nguyen, Hien M.; ACS Catalysis 9 (2019) 2110–; doi:10.1021/acscatal.8b04444

data_4514888
_publ_section_title
;
 Are Br\/onsted Acids the True Promoter of Metal-Triflate-Catalyzed
 Glycosylations? A Mechanistic Probe into 1,2-cis-Aminoglycoside Formation
 by Nickel Triflate
;
_journal_issue                   3
_journal_name_full               'ACS Catalysis'
_journal_page_first              2110
_journal_paper_doi               10.1021/acscatal.8b04444
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H26 F6 N2 O8'
_chemical_formula_sum            'C28 H26 F6 N2 O8'
_chemical_formula_weight         632.51
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7248(12)
_cell_length_b                   13.6488(13)
_cell_length_c                   19.0159(19)
_cell_measurement_reflns_used    9941
_cell_measurement_temperature    190(2)
_cell_measurement_theta_max      22.18
_cell_measurement_theta_min      2.53
_cell_volume                     3043.1(5)
_computing_cell_refinement       'APEX II Bruker AXS'
_computing_data_collection       'APEX II Bruker AXS'
_computing_data_reduction        'APEX II Bruker AXS'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'APEX II Bruker AXS'
_diffrn_ambient_temperature      190(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker-Nonius Kappa APEXII'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0569
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            90067
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.355
_diffrn_reflns_theta_min         2.985
_exptl_absorpt_coefficient_mu    0.124
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7093
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2008)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_description       plate
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.230
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1934 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

 One tri-flouro methyl group was disordered over three sites:
 C8 - F6, occ=0.369(3); C8' - F6', occ.=0.369(3);
 C8" - F6", occ.=0.261(6). The C-F distances were restrained
 to be the same as were the F--F distances. The anisotropic
 displacement parameters were restrained to be similar.

 One phenyl group was disordered over two sites:
 C9 - C14, occ.=0.739(6); C9' - c14', occ.=0.261(6).
 The anisotropic displacement parameters were restrained
 to be similar and the conformations were restrained
 to be the same.

;
_refine_ls_abs_structure_Flack   -0.2(2)
_refine_ls_extinction_coef       0.0035(7)
_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   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         7570
_refine_ls_number_restraints     545
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0439
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0380P)^2^+1.0112P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.793
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                5388
_reflns_number_total             7570
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04444_si_002.cif
_cod_data_source_block           ngu161
_cod_database_code               4514888
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.970
_shelx_estimated_absorpt_t_max   0.994
_shelx_res_checksum              55917
_shelx_hkl_checksum              19635