A New Silicon Lewis Acid for Highly Enantioselective Mannich Reactions of Aliphatic Ketone-Derived Hydrazones
Gregory T. Notte; James L. Leighton; Journal of the American Chemical Society 130 (2008) 6676–6677; doi:10.1021/ja800830h

data_4107806
_publ_section_title
;
 A New Silicon Lewis Acid for Highly Enantioselective Mannich Reactions of
 Aliphatic Ketone-Derived Hydrazones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6676
_journal_page_last               6677
_journal_paper_doi               10.1021/ja800830h
_journal_volume                  130
_journal_year                    2008
_chemical_absolute_configuration ad
_chemical_formula_sum            'C19 H19 Br N2 O5'
_chemical_formula_weight         435.27
_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                 91.413(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.4773(13)
_cell_length_b                   13.378(2)
_cell_length_c                   16.470(3)
_cell_measurement_reflns_used    9912
_cell_measurement_temperature    125(2)
_cell_measurement_theta_max      30.37
_cell_measurement_theta_min      2.40
_cell_volume                     1867.3(5)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      125(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_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  0.0347
_diffrn_reflns_av_sigmaI/netI    0.0510
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28961
_diffrn_reflns_theta_full        30.57
_diffrn_reflns_theta_max         30.57
_diffrn_reflns_theta_min         1.96
_exptl_absorpt_coefficient_mu    2.235
_exptl_absorpt_correction_T_max  0.7304
_exptl_absorpt_correction_T_min  0.5942
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.062
_refine_diff_density_min         -0.884
_refine_diff_density_rms         0.124
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.046(9)
_refine_ls_extinction_coef       0.0029(8)
_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   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         11381
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0588
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0944P)^2^+3.1605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1657
_refine_ls_wR_factor_ref         0.1762
_reflns_number_gt                9064
_reflns_number_total             11381
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja800830h-file001.cif
_cod_data_source_block           gns10
_cod_original_cell_volume        1867.4(5)
_cod_database_code               4107806