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_4022735
_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         'C26 H39 N2 O7'
_chemical_formula_sum            'C26 H39 N2 O7'
_chemical_formula_weight         491.59
_chemical_name_systematic
;
 ?
;
_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                 95.994(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            6
_cell_length_a                   22.169(4)
_cell_length_b                   6.5120(13)
_cell_length_c                   28.437(6)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25
_cell_measurement_theta_min      0
_cell_volume                     4082.8(14)
_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 0.901
_diffrn_measured_fraction_theta_max 0.901
_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  0.0561
_diffrn_reflns_av_sigmaI/netI    0.1414
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            31379
_diffrn_reflns_theta_full        28.40
_diffrn_reflns_theta_max         28.40
_diffrn_reflns_theta_min         0.92
_diffrn_standards_decay_%        0.0004
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.991
_exptl_absorpt_correction_T_min  0.979
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'XABS2 (PARKIN et al, 1995)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prismatic
_exptl_crystal_F_000             1590
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.302
_refine_diff_density_min         -0.214
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
Flack H D (1983), Acta Cryst. A39, 876-881
The absolute configuration was ascertain, with the 100 strongest Friedel 
pairs, using the Bijvoet module of Dirdif (Beurskens, 1999). 
The crystal structure contains three crystallographically independent 
molecules exhibiting the same chiral form.
The Bijvoet coeficient is 0.19(4) and the probability 1.000.
;
_refine_ls_abs_structure_Flack   -0.2(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     946
_refine_ls_number_reflns         16271
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1985
_refine_ls_R_factor_gt           0.1026
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0843P)^2^+0.4118P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1732
_refine_ls_wR_factor_ref         0.2108
_reflns_number_gt                8337
_reflns_number_total             16271
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo0622678si20061110_102038_1.cif
_cod_data_source_block           4c
_cod_depositor_comments
;
The following automatic conversions were performed:
'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to '/home/saulius/struct/CIF-dictionaries/cif_core.dic'
dictionary named 'cif_core.dic' version 2.4.1 from
2010-06-29.

'_exptl_absorpt_correction_type' value 'Empirical' changed to
'empirical' according to
'/home/saulius/struct/CIF-dictionaries/cif_core.dic' dictionary named
'cif_core.dic' version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_enum 1527 2010-12-29 10:47:43Z saulius 
;
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4022735