Asymmetric Diels-Alder and Ficini Reactions with Alkylidene β-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes: Mechanistic Insight
Christoph Schotes; Martin Althaus; Raphael Aardoom; Antonio Mezzetti; Journal of the American Chemical Society 134 (2012) 1331–1343; doi:10.1021/ja210372u

data_4117311
_publ_section_title
;
 Asymmetric Diels-Alder and Ficini Reactions with Alkylidene \b-Ketoesters
 Catalyzed by Chiral Ruthenium PNNP Complexes: Mechanistic Insight
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1331
_journal_page_last               1343
_journal_paper_doi               10.1021/ja210372u
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C53 H49 Cl4 F6 N2 O3 P3 Ru'
_chemical_formula_sum            'C53 H49 Cl4 F6 N2 O3 P3 Ru'
_chemical_formula_weight         1213.74
_chemical_name_common            '[Ru(3b-H)(PNNP)](PF6)'
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_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-97
_cell_angle_alpha                79.8090(10)
_cell_angle_beta                 70.1910(10)
_cell_angle_gamma                73.3450(10)
_cell_formula_units_Z            2
_cell_length_a                   13.3663(9)
_cell_length_b                   14.6427(10)
_cell_length_c                   14.7977(10)
_cell_measurement_reflns_used    7430
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.20
_cell_measurement_theta_min      2.16
_cell_volume                     2600.2(3)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SMART'
_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      100(2)
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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  0.0334
_diffrn_reflns_av_sigmaI/netI    0.0527
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26980
_diffrn_reflns_theta_full        28.27
_diffrn_reflns_theta_max         28.27
_diffrn_reflns_theta_min         1.46
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  0.9243
_exptl_absorpt_correction_T_min  0.7905
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   SADABS-2004/1
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.550
_exptl_crystal_description       prism
_exptl_crystal_F_000             1236
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.018
_refine_diff_density_min         -1.016
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     671
_refine_ls_number_reflns         12775
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0544
_refine_ls_R_factor_gt           0.0440
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0456P)^2^+2.5497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1043
_reflns_number_gt                10837
_reflns_number_total             12775
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja210372u_si_002.cif
_cod_data_source_block           new3
_cod_original_cell_volume        2600.3(3)
_cod_database_code               4117311