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_4103442
_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 H34 O10'
_chemical_formula_weight         494.52
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_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                 111.143(15)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.8813(15)
_cell_length_b                   9.4783(10)
_cell_length_c                   13.659(4)
_cell_measurement_temperature    293(2)
_cell_volume                     1313.9(5)
_computing_cell_refinement       'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs 1990-2000)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR92(Altomare et al., 1994)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       '95mm CCD camera on \k-goniostat'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0682
_diffrn_reflns_av_sigmaI/netI    0.1196
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14848
_diffrn_reflns_theta_full        30.00
_diffrn_reflns_theta_max         30.00
_diffrn_reflns_theta_min         2.98
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       parallelepiped
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.1(11)
_refine_ls_extinction_coef       0.025(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.938
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         6665
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.938
_refine_ls_R_factor_all          0.1376
_refine_ls_R_factor_gt           0.0571
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0670P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1403
_reflns_number_gt                3561
_reflns_number_total             6665
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja1054065_si_002.cif
_cod_data_source_block           shelxl
_cod_database_code               4103442