Squaramide-catalyzed asymmetric Mannich reactions between 3-fluorooxindoles and pyrazolinone ketimines.
Zhang, Qing-Da; Zhao, Bo-Liang; Li, Bing-Yu; Du, Da-Ming; Organic & biomolecular chemistry 17 (2019) 7182–7191; doi:10.1039/c9ob01350d

data_7156965
_publ_section_title
;
 Squaramide-catalyzed asymmetric Mannich reactions between
 3-fluorooxindoles and pyrazolinone ketimines.
;
_journal_issue                   30
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7182
_journal_page_last               7191
_journal_paper_doi               10.1039/c9ob01350d
_journal_volume                  17
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H20 Br F N4 O2'
_chemical_formula_sum            'C25 H20 Br F N4 O2'
_chemical_formula_weight         507.36
_chemical_melting_point          437.0(10)
_chemical_name_systematic
(S)-3-((S)-4-((2-Bromophenyl)amino)-3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)-3-fluoro-1-methylindolin-2-one
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-25 deposited with the CCDC.    2019-07-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4813(13)
_cell_length_b                   16.177(3)
_cell_length_c                   21.944(4)
_cell_measurement_reflns_used    6736
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      27.4855
_cell_measurement_theta_min      2.2429
_cell_volume                     2300.8(8)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      153.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'multiwire proportional'
_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  0.0472
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            15376
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         2.684
_exptl_absorpt_coefficient_mu    1.825
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8144
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: petroleum ether/ethyl acetate'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.266
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1833 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         5247
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0400
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0327P)^2^+0.5204P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0857
_refine_ls_wR_factor_ref         0.0877
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                4947
_reflns_number_total             5247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01350d2.cif
_cod_data_source_block           bwn19089
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value '436-438' was changed to '437.0(10)'
- the average value was taken and precision was estimated.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 7156965.cif.
;
_cod_original_cell_volume        2300.7(8)
_cod_database_code               7156965
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.669
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N3(H3)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4), C5(H5), C16(H16), C17(H17), C18(H18), C19(H19),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C13(H13A,H13B,H13C)
;
_olex2_submission_special_instructions 'No special instructions were received'