Direct enantio- and diastereoselective Mannich reactions of isatin-derived ketimines with oxo-indanecarboxylates catalyzed by chiral thiourea derived from hydroquinidine.
Liu, Yuxin; Wang, Jingdong; Wei, Zhonglin; Cao, Jungang; Liang, Dapeng; Lin, Yingjie; Duan, Haifeng; Organic & biomolecular chemistry 16 (2018) 8927–8932; doi:10.1039/c8ob02595a

data_7156569
_publ_section_title
;
 Direct enantio- and diastereoselective Mannich reactions of
 isatin-derived ketimines with oxo-indanecarboxylates catalyzed by chiral
 thiourea derived from hydroquinidine.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8927
_journal_page_last               8932
_journal_paper_doi               10.1039/c8ob02595a
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration unk
_chemical_formula_moiety         '0.07(C31 H29 N2 O6)'
_chemical_formula_sum            'C2.3 H2.15 N0.15 O0.44'
_chemical_formula_weight         38.93
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-08-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_audit_update_record
;
2018-08-22 deposited with the CCDC.
2018-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            54
_cell_length_a                   8.4217(6)
_cell_length_b                   17.9017(12)
_cell_length_c                   18.0406(12)
_cell_measurement_reflns_used    2541
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      20.03
_cell_measurement_theta_min      2.28
_cell_volume                     2719.9(3)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v6.45A (Bruker, 2003)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            15678
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.38
_diffrn_reflns_theta_min         1.60
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.747111
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) was 0.0395 before and 0.0243 after correction.
The Ratio of minimum to maximum transmission is 0.7471.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.001
_exptl_crystal_size_mid          0.001
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.3(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     356
_refine_ls_number_reflns         5572
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.1000
_refine_ls_R_factor_gt           0.0611
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0954P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1507
_refine_ls_wR_factor_ref         0.1736
_reflns_number_gt                3561
_reflns_number_total             5572
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8ob02595a2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7156569.cif.'
_cod_original_formula_sum        'C2.30 H2.15 N0.15 O0.44'
_cod_database_code               7156569
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C31, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, C31
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O6, C31
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C31) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
4.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C2(H2A), C17(H17), C5(H5), C3(H3), C11(H11), C15(H15), C14(H14),
 C4(H4), C13(H13), C12(H12), C21(H21), C22(H22), C20(H20), C23(H23)
4.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C)
;
_olex2_submission_special_instructions 'No special instructions were received'