Asymmetric synthesis of 3,3'-pyrrolidinyl-dispirooxindoles via a one-pot organocatalytic Mannich/deprotection/aza-Michael sequence.
Zhao, Kun; Zhi, Ying; Li, Xinyi; Puttreddy, Rakesh; Rissanen, Kari; Enders, Dieter; Chemical communications (Cambridge, England) 52 (2016) 2249–2252; doi:10.1039/c5cc10057g

data_7118232
_publ_section_title
;
 Asymmetric synthesis of 3,3'-pyrrolidinyl-dispirooxindoles via a one-pot
 organocatalytic Mannich/deprotection/aza-Michael sequence.
;
_journal_issue                   11
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2249
_journal_page_last               2252
_journal_paper_doi               10.1039/c5cc10057g
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H26 Br N3 O4, 0.5(C4 H8 O2)'
_chemical_formula_sum            'C31 H30 Br N3 O5'
_chemical_formula_weight         604.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_symmetry_space_group_name_Hall  'I 2y'
_symmetry_space_group_name_H-M   'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-11-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2015-12-04 deposited with the CCDC.
2015-12-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0030(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6406(2)
_cell_length_b                   9.57209(15)
_cell_length_c                   19.5953(3)
_cell_measurement_reflns_used    13352
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      74.1360
_cell_measurement_theta_min      4.5160
_cell_volume                     2725.62(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1977
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -67.00   27.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
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  2 omega  -38.00  -13.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013  -60.0000   24.0000 25

  3 omega -109.00  -71.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013  -60.0000   24.0000 38

  4 omega -112.00   -4.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013  -19.0000 -180.0000 108

  5 omega  -45.00   32.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013   37.0000 -180.0000 77

  6 omega  -47.00   33.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
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  7 omega   10.00   38.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
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  8 omega    9.00   76.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
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  9 omega   11.00   74.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9013   77.0000  -60.0000 63

 10 omega    6.00   82.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
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 11 omega    9.00   65.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9013   77.0000 -150.0000 56

 12 omega    9.00   94.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9013   77.0000   90.0000 85

 13 omega  126.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  -90.0000 52

 14 omega   74.00  123.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000   30.0000 49

 15 omega   74.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  -90.0000 26

 16 omega   33.00   99.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -94.0000  -90.0000 66

 17 omega   74.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000 -150.0000 26

 18 omega   34.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601 -125.0000   90.0000 88

 19 omega   76.00  173.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   71.0000   51.0142 97

 20 omega   78.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000  -90.0000 26

 21 omega   74.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  120.0000 104

 22 omega   25.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -94.0000 -180.0000 83

 23 omega   74.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000   90.0000 27

 24 omega   74.00  174.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  -30.0000 100

 25 omega   74.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000    0.0000 26

 26 omega  112.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000    0.0000 66

 27 omega   29.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -94.0000   90.0000 75

 28 omega   78.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000  150.0000 26

 29 omega   78.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000 -180.0000 32

 30 omega   35.00   99.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -94.0000  -30.0000 64

 31 omega   74.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000   60.0000 26

 32 omega  116.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  150.0000 62

 33 omega   78.00  134.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000  -30.0000 56

 34 omega   74.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  -60.0000 28

 35 omega   78.00  139.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000 -150.0000 61

 36 omega   74.00  134.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000 -180.0000 60

 37 omega   78.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000  -60.0000 63

 38 omega   74.00  172.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000 -120.0000 98

 39 omega   74.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   77.0000  150.0000 26

 40 omega   80.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000   90.0000 86

 41 omega   78.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   61.0000   30.0000 29

 42 omega   77.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   71.0000  109.1421 25

 43 omega   74.00  143.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   76.0000 -135.0350 69

 44 omega   77.00  103.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601   63.0000   -0.2119 26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0667996000
_diffrn_orient_matrix_UB_12      -0.1248982000
_diffrn_orient_matrix_UB_13      0.0041176000
_diffrn_orient_matrix_UB_21      0.0508952000
_diffrn_orient_matrix_UB_22      0.0667718000
_diffrn_orient_matrix_UB_23      -0.0561623000
_diffrn_orient_matrix_UB_31      0.0647321000
_diffrn_orient_matrix_UB_32      0.0764690000
_diffrn_orient_matrix_UB_33      0.0556779000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21605
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.750
_diffrn_reflns_theta_max         66.719
_diffrn_reflns_theta_min         3.568
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.443
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64505
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       needle
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.2763
_exptl_crystal_size_mid          0.0489
_exptl_crystal_size_min          0.0371
_refine_diff_density_max         0.467
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 2127 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.025(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         4842
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0295
_refine_ls_R_factor_gt           0.0279
_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^)+(0.0403P)^2^+1.5426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0724
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.877
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4668
_reflns_number_total             4842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc10057g2.cif
_cod_data_source_block           7d
_cod_depositor_comments          'Adding full bibliography for 7118232.cif.'
_cod_database_code               7118232
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C10 H10 N1 O1'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C32-C33
 1.54 with sigma of 0.01
 C32-O1
 1.43 with sigma of 0.01
 C31-O1
 1.43 with sigma of 0.01
3. Others
 Fixed Sof: C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C31(0.5) C32(0.5) H32A(0.5)
 H32B(0.5) C33(0.5) H33A(0.5) H33B(0.5) H33C(0.5) O1(0.5) O2(0.5)
4.a Ternary CH refined with riding coordinates:
 C5(H5)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C6(H6A,H6B), C23(H23A,H23B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C17(H17), C18(H18), C19(H19), C20(H20),
 C25(H25), C26(H26), C28(H28), C29(H29), N3(H3)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              49851
_shelx_hkl_checksum              91849
_olex2_submission_special_instructions 'No special instructions were received'