Enantiodivergent Synthesis of Bis-Spiropyrrolidines via Sequential Interrupted and Completed (3 + 2) Cycloadditions.
Conde, Egoitz; Rivilla, Iván; Larumbe, Amaia; Cossío, Fernando P; The Journal of organic chemistry 80 (2015) 11755–11767; doi:10.1021/acs.joc.5b01418

data_4036290
_publ_section_title
;
 Enantiodivergent Synthesis of Bis-Spiropyrrolidines via Sequential
 Interrupted and Completed (3 + 2) Cycloadditions.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11755
_journal_page_last               11767
_journal_paper_doi               10.1021/acs.joc.5b01418
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C11 H14 N2 O2'
_chemical_formula_sum            'C11 H14 N2 O2'
_chemical_formula_weight         206.24
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-01-19T12:43:09-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 93.485(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.3134(2)
_cell_length_b                   8.1507(2)
_cell_length_c                   12.0605(4)
_cell_measurement_reflns_used    3630
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.285
_cell_measurement_theta_min      6.529
_cell_measurement_wavelength     1.54184
_cell_volume                     521.35(3)
_computing_cell_refinement       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_collection       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_reduction        'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_molecular_graphics    'Diamond v.3.2f (Crystal Impact GbR, 2008)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov et al, 2010)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_diffrn_measurement_details
;
  1 omega -104.00  -48.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256 -162.0000  -13.0000 56

  2 omega   18.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   55.0000   -7.0000 97

  3 omega  -30.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256  -55.0000 -150.0000 88

  4 omega   22.00   72.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   37.0000  120.0000 50

  5 omega  -71.00  -44.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000  -90.0000 27

  6 omega  -94.00  -55.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -45.0000  120.0000 39

  7 omega  -87.00  -61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   77.0000  120.0000 26

  8 omega  -96.00  -55.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000   90.0000 41

  9 omega   41.00   71.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -150.0000 30

 10 omega   48.00   77.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   30.0000 29

 11 omega   85.00  142.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  120.0000 57

 12 omega   38.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  150.0000 25

 13 omega   39.00   70.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -60.0000 31

 14 omega   38.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -120.0000 25

 15 omega   96.00  122.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000   30.0000 26

 16 omega   44.00   71.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   90.0000 27

 17 omega  117.00  148.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   60.0000 31

 18 omega   36.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   60.0000 25

 19 omega   36.00   99.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000 -180.0000 63

 20 omega   84.00  112.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   60.0000 28

 21 omega   35.00   65.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  -30.0000 30

 22 omega   84.00  158.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -60.0000 74

 23 omega   65.00   97.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000 -120.0000 32

 24 omega   83.00  113.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 30

 25 omega  121.00  157.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 36

 26 omega   36.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  150.0000 25

 27 omega   29.00   56.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000 -120.0000 27

 28 omega  104.00  158.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000   30.0000 54

 29 omega   89.00  115.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  120.0000 26

 30 omega  124.00  149.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  -90.0000 25

 31 omega   41.00   71.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -90.0000 30

 32 omega  -88.00  -23.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  111.0000  150.0000 65

 33 omega   84.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 25

 34 omega  130.00  156.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  -30.0000 26

 35 omega   59.00  103.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000   90.0000 44

 36 omega   56.00   82.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000    0.0000 26

 37 omega   91.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -120.0000 25

 38 omega   53.00   81.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 28

 39 omega   59.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -60.0000 50

 40 omega -115.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000 -150.0000 104

 41 omega  -70.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256   57.0000    0.0000 103

 42 omega   11.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   57.0000 -120.0000 104

 43 omega    2.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256 -125.0000 -150.0000 96

 44 omega    7.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   77.0000   30.0000 86

 45 omega    7.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   77.0000  120.0000 113

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0069519
_diffrn_orient_matrix_UB_12      0.0243417
_diffrn_orient_matrix_UB_13      -0.1264602
_diffrn_orient_matrix_UB_21      0.2200702
_diffrn_orient_matrix_UB_22      -0.1227624
_diffrn_orient_matrix_UB_23      -0.0025153
_diffrn_orient_matrix_UB_31      -0.1893979
_diffrn_orient_matrix_UB_32      -0.1416502
_diffrn_orient_matrix_UB_33      -0.0195519
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            5983
_diffrn_reflns_theta_full        69.97
_diffrn_reflns_theta_max         69.97
_diffrn_reflns_theta_min         3.67
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.749
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.886
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
        (compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             220
_exptl_crystal_size_max          0.2055
_exptl_crystal_size_mid          0.0878
_exptl_crystal_size_min          0.0416
_refine_diff_density_max         0.154
_refine_diff_density_min         -0.131
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (99%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2011).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-12. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.04(14), which together with Flack parameter 
value, indicate that the absolute structure has sureley been determined 
correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717

;
_refine_ls_abs_structure_Flack   -0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.08
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         1972
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.08
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0306
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0321P)^2^+0.0617P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.073
_refine_ls_wR_factor_ref         0.0743
_reflns_number_gt                1881
_reflns_number_total             1972
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo5b01418_si_003.cif
_cod_data_source_block           a20150014_ps65
_cod_database_code               4036290