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_4036288
_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         'C25 H22 F1 N3 O3'
_chemical_formula_sum            'C25 H22 F N3 O3'
_chemical_formula_weight         431.46
_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             2014-10-22T11:08:05-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90.4040(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3132(2)
_cell_length_b                   6.54060(10)
_cell_length_c                   22.9007(3)
_cell_measurement_reflns_used    19481
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.244
_cell_measurement_theta_min      3.591
_cell_measurement_wavelength     1.54184
_cell_volume                     2143.84(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega -117.00  -18.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -77.0000  120.0000 99

  2 omega  -20.00   79.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506  -99.0000   60.0000 99

  3 omega  -76.00  -50.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000   90.0000 26

  4 omega   43.00   69.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -90.0000 26

  5 omega   35.00   69.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -180.0000 34

  6 omega   30.00   55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000    0.0000 25

  7 omega   46.00   72.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -120.0000 26

  8 omega   35.00   65.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -150.0000 30

  9 omega   41.00   67.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  -90.0000 26

 10 omega   36.00   68.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  150.0000 32

 11 omega   41.00  120.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000   60.0000 79

 12 omega   47.00  146.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -120.0000 99

 13 omega   79.00  144.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000 -120.0000 65

 14 omega  -67.00   33.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506   37.0000  -90.0000 100

 15 omega   29.00   83.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506 -125.0000  -30.0000 54

 16 omega  -53.00  -26.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000 -120.0000 27

 17 omega -133.00  -81.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -94.0000 -180.0000 52

 18 omega -160.00 -134.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -111.0000   60.0000 26

 19 omega   57.00  157.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000   60.0000 100

 20 omega   95.00  122.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -126.0000   16.0000 27

 21 omega   62.00   95.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000   90.0000 33

 22 omega  119.00  157.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -60.0000 38

 23 omega   35.00   69.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  120.0000 34

 24 omega   35.00   61.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   30.0000 26

 25 omega   89.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -150.0000 27

 26 omega   38.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 78

 27 omega   46.00   77.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000    0.0000 31

 28 omega  131.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -120.0000 27

 29 omega   77.00  111.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -180.0000 34

 30 omega  112.00  139.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  -60.0000 27

 31 omega   50.00  101.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  150.0000 51

 32 omega -115.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -57.0000   30.0000 104

 33 omega -120.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -77.0000  -90.0000 113

 34 omega -115.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -57.0000  -60.0000 104

 35 omega  -75.00   38.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506   77.0000  -60.0000 113

 36 omega -115.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -57.0000 -180.0000 104

 37 omega   63.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506  143.0000  -97.0000 51

 38 omega -162.00 -126.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   60.0000 36

 39 omega -157.00  -53.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000  150.0000 104

 40 omega -157.00  -53.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000   90.0000 104

 41 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -30.0000 113

 42 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   30.0000 113

 43 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 113

 44 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -150.0000 113

 45 omega   83.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -120.0000 75

 46 omega   85.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -150.0000 73

 47 omega   35.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 81

 48 omega   85.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000   60.0000 73

 49 omega   79.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  150.0000 79

 50 omega   83.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -30.0000 75

 51 omega   82.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000  120.0000 76

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0367277
_diffrn_orient_matrix_UB_12      -0.1731282
_diffrn_orient_matrix_UB_13      0.0392774
_diffrn_orient_matrix_UB_21      0.0198722
_diffrn_orient_matrix_UB_22      0.1316188
_diffrn_orient_matrix_UB_23      0.0544809
_diffrn_orient_matrix_UB_31      -0.0991864
_diffrn_orient_matrix_UB_32      0.0903932
_diffrn_orient_matrix_UB_33      -0.0041146
_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  0.0471
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            41593
_diffrn_reflns_theta_full        72.5
_diffrn_reflns_theta_max         72.5
_diffrn_reflns_theta_min         3.09
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.782
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_correction_T_min  0.898
_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            colourless
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.1832
_exptl_crystal_size_mid          0.0838
_exptl_crystal_size_min          0.0733
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.035
_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 10-42. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=0.04(7), 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   -0.09(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     586
_refine_ls_number_reflns         8443
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0446P)^2^+0.5635P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0938
_reflns_number_gt                7931
_reflns_number_total             8443
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo5b01418_si_002.cif
_cod_data_source_block           a2014413_ps56
_cod_database_code               4036288