Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates: Enantioselective Three-Component Asymmetric Aza-Diels-Alder Reactions of Cyclic Ketones.
Deng, Yongming; Karunaratne, Chamini V.; Csatary, Erika; Tierney, David L.; Wheeler, Kraig; Wang, Hong; The Journal of organic chemistry 80 (2015) 7984–7993; doi:10.1021/acs.joc.5b00895

data_4036222
_publ_section_title
;
 Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates:
 Enantioselective Three-Component Asymmetric Aza-Diels-Alder Reactions of
 Cyclic Ketones.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7984
_journal_page_last               7993
_journal_paper_doi               10.1021/acs.joc.5b00895
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C80 H48 O22 P4 Y2, 2(C F3 O3 S), 8(C4 H8 O2), 6(C6 H14)'
_chemical_formula_sum            'C138 H168 F6 O44 P4 S2 Y2'
_chemical_formula_weight         3183.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 95.062(1)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.0610(5)
_cell_length_b                   17.2598(7)
_cell_length_c                   23.1595(6)
_cell_measurement_reflns_used    9831
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.229
_cell_measurement_theta_min      2.560
_cell_volume                     6793.2(4)
_computing_cell_refinement       APEX2
_computing_data_collection       APEX2
_computing_data_reduction
;
SAINT (Bruker, 2010) and XPREP (Bruker, 2010)
;
_computing_molecular_graphics    'XSEED (Barbour, 2001)'
_computing_publication_material  'XSEED (Barbour, 2001)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXL-2014 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEXII CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            100027
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         1.915
_exptl_absorpt_coefficient_mu    2.613
_exptl_absorpt_correction_T_max  0.589
_exptl_absorpt_correction_T_min  0.126
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2013)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description       'transparent plate'
_exptl_crystal_F_000             2744
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.176
_platon_squeeze_details
;
 Entries 4 and 6 were ingnored due to low electron density.  
 With P2~1~ and Z=2, the 388 electrons correspond to 194 
 electrons (388 electrons/2 = 194) in the asymmetric unit.
 Both dioxane (48 electrons) and hexane (50 electrons) were
 used as the recrystallization solvent system.  Given each 
 solvent has approx 50 electrons (8 electrons for Oxygen, 
 6 for Carbon, and 1for Hydrogen), then 194/50 = 3.9 solvent 
 molecules per asymmetric unit.  The results are
 inconclusive as to the identity of the solvent trapped
 in the crystal.  The molecular formula reflects hexane
 as the inclusion solvent.
;
_refine_diff_density_max         1.093
_refine_diff_density_min         -1.410
_refine_diff_density_rms         0.166
_refine_ls_abs_structure_details
;
 Flack x determined using 8270 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.052(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.484
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1293
_refine_ls_number_reflns         22568
_refine_ls_number_restraints     1516
_refine_ls_restrained_S_all      1.470
_refine_ls_R_factor_all          0.1205
_refine_ls_R_factor_gt           0.1152
_refine_ls_shift/su_max          0.063
_refine_ls_shift/su_mean         0.014
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3054
_refine_ls_wR_factor_ref         0.3176
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.816
_reflns_Friedel_fraction_max     0.814
_reflns_number_gt                20364
_reflns_number_total             22568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00895_si_003.cif
_cod_data_source_block           hwang18
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4036222
_shelx_estimated_absorpt_t_min   0.0404
_shelx_estimated_absorpt_t_max   0.631
_shelxl_version_number           2014-3
_shelx_res_checksum              80074
_shelx_hkl_checksum              29948