Rh(II) Carbene-Promoted Activation of the Anomeric C-H Bond of Carbohydrates: A Stereospecific Entry toward α- and β-Ketopyranosides
Mélissa Boultadakis-Arapinis; Pascale Lemoine; Serge Turcaud; Laurent Micouin; Thomas Lecourt; Journal of the American Chemical Society 132 (2010) 15477–15479; doi:10.1021/ja1054065

data_4103441
_publ_section_title
;
 Rh(II) Carbene-Promoted Activation of the Anomeric C-H Bond of
 Carbohydrates: A Stereospecific Entry toward \a- and \b-Ketopyranosides
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15477
_journal_page_last               15479
_journal_paper_doi               10.1021/ja1054065
_journal_volume                  132
_journal_year                    2010
_chemical_formula_sum            'C25 H0.25 O7.5'
_chemical_formula_weight         420.50
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.121(2)
_cell_length_b                   14.951(5)
_cell_length_c                   23.343(5)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      7.13
_cell_measurement_theta_min      2.61
_cell_volume                     2136.2(11)
_computing_cell_refinement       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_collection       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_reduction        'XCAD4 (Harms & Wocadlo, 1995)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR92(Altomare et al., 1994)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Enraf-nonius CAD4'
_diffrn_measurement_method       '\w - 2\q'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1512
_diffrn_reflns_av_sigmaI/netI    0.1094
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            24654
_diffrn_reflns_theta_full        30.08
_diffrn_reflns_theta_max         30.08
_diffrn_reflns_theta_min         1.62
_diffrn_standards_decay_%        none
_diffrn_standards_interval_time  60
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       parallelepiped
_exptl_crystal_F_000             841
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.172
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.7(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.899
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         6251
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.899
_refine_ls_R_factor_all          0.1628
_refine_ls_R_factor_gt           0.0411
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0442P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0776
_refine_ls_wR_factor_ref         0.1038
_reflns_number_gt                2737
_reflns_number_total             6251
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1054065_si_001.cif
_cod_data_source_block           shelxl
_cod_original_sg_symbol_H-M      'P 21 21 21 '
_cod_original_formula_sum        'C25 H0.25 O7.50'
_cod_database_code               4103441