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_4117312
_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 H51 Cl5 F6 N2 O3 P3 Ru'
_chemical_formula_sum            'C53 H51 Cl5 F6 N2 O3 P3 Ru'
_chemical_formula_weight         1249.19
_chemical_name_common            '[Ru(3b-H)(PNNP)](PF6) (minor) (5c)'
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 95.133(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.4554(14)
_cell_length_b                   14.350(2)
_cell_length_c                   35.366(5)
_cell_measurement_reflns_used    5112
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.44
_cell_measurement_theta_min      2.24
_cell_volume                     5284.9(13)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'BRUKER APEX'
_diffrn_measurement_method       '\w 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  0.0804
_diffrn_reflns_av_sigmaI/netI    0.0656
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            41090
_diffrn_reflns_theta_full        25.05
_diffrn_reflns_theta_max         25.05
_diffrn_reflns_theta_min         1.16
_exptl_absorpt_coefficient_mu    0.707
_exptl_absorpt_correction_T_max  0.9044
_exptl_absorpt_correction_T_min  0.8174
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   SADABS-2004/1
_exptl_crystal_colour            'red orange'
_exptl_crystal_density_diffrn    1.570
_exptl_crystal_description       prism
_exptl_crystal_F_000             2540
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.290
_refine_diff_density_min         -1.069
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     762
_refine_ls_number_reflns         9340
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.184
_refine_ls_R_factor_all          0.1043
_refine_ls_R_factor_gt           0.0818
_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^)+(0.0448P)^2^+26.3564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1602
_refine_ls_wR_factor_ref         0.1692
_reflns_number_gt                7501
_reflns_number_total             9340
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja210372u_si_003.cif
_cod_data_source_block           new9
_cod_database_code               4117312