Bifunctional Squaramide-Catalyzed Asymmetric [3 + 2] Cyclization of 2-(1-Methyl-2-oxoindolin-3-yl)malononitriles with Unsaturated Pyrazolones To Construct Spirooxindole-Fused Spiropyrazolones.
Lin, Ye; Zhao, Bo-Liang; Du, Da-Ming; The Journal of organic chemistry 84 (2019) 10209–10220; doi:10.1021/acs.joc.9b01268

data_4034011
_publ_section_title
;
 Bifunctional Squaramide-Catalyzed Asymmetric [3 + 2] Cyclization of
 2-(1-Methyl-2-oxoindolin-3-yl)malononitriles with Unsaturated Pyrazolones
 To Construct Spirooxindole-Fused Spiropyrazolones.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10209
_journal_page_last               10220
_journal_paper_doi               10.1021/acs.joc.9b01268
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H22 Br N5 O2, C4 H8 O2'
_chemical_formula_sum            'C33 H30 Br N5 O4'
_chemical_formula_weight         640.53
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.207(3)
_cell_length_b                   13.296(3)
_cell_length_c                   34.839(7)
_cell_measurement_reflns_used    15657
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      27.4855
_cell_measurement_theta_min      1.5316
_cell_volume                     6118(2)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      153.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.994
_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  0.0400
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            36577
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.173
_exptl_absorpt_coefficient_mu    1.390
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8323
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.552
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 4467 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     783
_refine_ls_number_reflns         13907
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0333P)^2^+0.9975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0950
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                12635
_reflns_number_total             13907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01268_si_002.cif
_cod_data_source_block           bwn19065
_cod_database_code               4034011
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.697
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N3(H3A,H3B), N8(H8A,H8B)
2.b Ternary CH refined with riding coordinates:
 C7(H7), C36(H36)
2.c Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C64(H64A,H64B)
2.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32), C34(H34),
  C35(H35), C39(H39), C40(H40), C41(H41), C42(H42), C54(H54), C55(H55),
 C56(H56), C57(H57), C58(H58)
2.e Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C23(H23A,H23B,H23C), C44(H44A,H44B,H44C), C52(H52A,H52B,
 H52C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C66(H66A,
 H66B,H66C)
;
_olex2_submission_special_instructions 'No special instructions were received'