Asymmetric α-amination of 4-substituted pyrazolones catalyzed by a chiral Gd(OTf)3/N,N'-dioxide complex: highly enantioselective synthesis of 4-amino-5-pyrazolone derivatives.
Yang, Zhigang; Wang, Zhen; Bai, Sha; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming; Organic letters 13 (2011) 596–599; doi:10.1021/ol102804p

data_1501911
_publ_section_title
;
 Asymmetric \a-amination of 4-substituted pyrazolones catalyzed by a
 chiral Gd(OTf)3/N,N'-dioxide complex: highly enantioselective synthesis
 of 4-amino-5-pyrazolone derivatives.
;
_journal_issue                   4
_journal_name_full               'Organic letters'
_journal_page_first              596
_journal_page_last               599
_journal_paper_doi               10.1021/ol102804p
_journal_volume                  13
_journal_year                    2011
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H26 N4 O5'
_chemical_formula_sum            'C23 H26 N4 O5'
_chemical_formula_weight         438.48
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 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                 122.269(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.639(3)
_cell_length_b                   13.026(2)
_cell_length_c                   12.1899(18)
_cell_measurement_reflns_used    13879
_cell_measurement_temperature    294(2)
_cell_measurement_theta_max      68.22
_cell_measurement_theta_min      3.12
_cell_volume                     2368.2(7)
_computing_cell_refinement       'Rapid Auto Ver 2.30(Rigaku 1998)'
_computing_data_collection       'Rapid Auto Ver 2.30(Rigaku 1998)'
_computing_data_reduction        'Rapid Auto Ver 2.30(Rigaku 1998)'
_computing_molecular_graphics    'XP in Siemens SHELXTL (Sheldrick, 1994)'
_computing_publication_material  'SHELX97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      294(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku raxis Rapid IP Area Detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0415
_diffrn_reflns_av_sigmaI/netI    0.0368
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13879
_diffrn_reflns_theta_full        68.23
_diffrn_reflns_theta_max         68.23
_diffrn_reflns_theta_min         4.29
_exptl_absorpt_coefficient_mu    0.726
_exptl_absorpt_correction_T_max  0.7221
_exptl_absorpt_correction_T_min  0.6618
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'NUMABS by T.Higashi Jun 3, 2003'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.62
_exptl_crystal_size_mid          0.54
_exptl_crystal_size_min          0.48
_refine_diff_density_max         0.151
_refine_diff_density_min         -0.138
_refine_diff_density_rms         0.026
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.5(3)
_refine_ls_extinction_coef       0.00211(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         4148
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.181
_refine_ls_R_factor_all          0.0697
_refine_ls_R_factor_gt           0.0591
_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^)+(0.0423P)^2^+1.1765P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1262
_refine_ls_wR_factor_ref         0.1316
_reflns_number_gt                3473
_reflns_number_total             4148
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol102804p_si_001.cif
_cod_data_source_block           sx2895
_cod_original_cell_volume        2368.3(6)
_cod_original_sg_symbol_H-M      C2
_cod_database_code               1501911