Highly Enantioselective Electrophilic Amination and Michael Addition of Cyclic β-Ketoesters Induced by Lanthanides and (S,S)-ip-pybox: The Mechanism
Josep Comelles; Àlex Pericas; Marcial Moreno-Mañas; Adelina Vallribera; Galí Drudis-Solé; Agusti Lledos; Teodor Parella; Anna Roglans; Santiago García-Granda; Laura Roces-Fernández; Journal of Organic Chemistry 72 (2007) 2077–2087; doi:10.1021/jo0622678

data_4022736
_publ_section_title
;
 Highly Enantioselective Electrophilic Amination and Michael
 Addition of Cyclic \b-Ketoesters Induced by Lanthanides and
 (S,S)-ip-pybox: The Mechanism
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              2077
_journal_page_last               2087
_journal_paper_doi               10.1021/jo0622678
_journal_volume                  72
_journal_year                    2007
_chemical_compound_source        synthesis
_chemical_formula_moiety         'C21 H31 N5 O6'
_chemical_formula_sum            'C21 H31 N5 O6'
_chemical_formula_weight         449.51
_space_group_IT_number           1
_symmetry_cell_setting           triclinic
_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                87.6480(10)
_cell_angle_beta                 80.5070(10)
_cell_angle_gamma                71.0880(10)
_cell_formula_units_Z            2
_cell_length_a                   9.1937(5)
_cell_length_b                   11.5288(6)
_cell_length_c                   12.5921(7)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25
_cell_measurement_theta_min      0
_cell_volume                     1245.22(12)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.867
_diffrn_measured_fraction_theta_max 0.867
_diffrn_measurement_device_type  'Bruker-siemens smart CCD diffractometer'
_diffrn_measurement_method       '\w-2\q scan technique'
_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  0.0184
_diffrn_reflns_av_sigmaI/netI    0.0643
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14042
_diffrn_reflns_theta_full        29.50
_diffrn_reflns_theta_max         29.50
_diffrn_reflns_theta_min         1.64
_diffrn_standards_decay_%        -0.0006
_diffrn_standards_interval_count 200
_diffrn_standards_interval_time  60
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.979
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'XABS2 (PARKIN et al., 1995)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.356
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack H D (1983), Acta Cryst. A39, 876-881
 The absolute configuration was ascertain, with the 38 strongest Friedel 
pairs, using the Bijvoet module of Dirdif (Beurskens, 1999). 
The crystal structure contains two crystallographically independent molecules 
exhibiting the same chiral form.
The Bijvoet coeficient is 0.13(5) and the probability 1.000.
;
_refine_ls_abs_structure_Flack   0(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         10317
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1531
_refine_ls_R_factor_gt           0.0889
_refine_ls_shift/su_max          0.496
_refine_ls_shift/su_mean         0.074
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0934P)^2^+0.3780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1868
_refine_ls_wR_factor_ref         0.2180
_reflns_number_gt                5689
_reflns_number_total             10317
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo0622678si20061110_102038_2.cif
_cod_data_source_block           6
_cod_depositor_comments
;
The following automatic conversions were performed:
'_geom_bond_publ_flag' value 'YES' changed to 'yes' according to
'/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29 (129
times).

'_geom_angle_publ_flag' value 'YES' changed to 'yes' according to
'/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29 (236
times).

'_geom_torsion_publ_flag' value 'YES' changed to 'yes' according
to '/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29 (112 times).

Automatic conversion script
Id: cif_fix_enum 1527 2010-12-29 10:47:43Z saulius 
;
_cod_original_sg_symbol_Hall     P1
_cod_database_code               4022736