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_4036289
_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         'C31 H28 N2 O5 S2, 0.5(C6 H14)'
_chemical_formula_sum            'C34 H35 N2 O5 S2'
_chemical_formula_weight         615.78
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-08T12:02:35-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.0236(5)
_cell_length_b                   20.7843(16)
_cell_length_c                   22.7086(18)
_cell_measurement_reflns_used    1995
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.277
_cell_measurement_theta_min      3.97
_cell_measurement_wavelength     1.54184
_cell_volume                     6146.9(7)
_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, 2009)'
_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 -113.00  -11.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756  -57.0000 -180.0000 102

  2 omega  -17.00   56.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756  -38.0000  -30.0000 73

  3 omega -157.00 -107.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -125.0000 -120.0000 50

  4 omega   34.00   77.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000   30.0000 43

  5 omega   31.00   69.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  150.0000 38

  6 omega   30.00   69.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   90.0000 39

  7 omega   32.00   98.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000    0.0000 66

  8 omega   35.00   72.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -30.0000 37

  9 omega   24.00  108.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000   60.0000 84

 10 omega   35.00   69.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  120.0000 34

 11 omega   32.00   67.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -180.0000 35

 12 omega   36.00   69.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -150.0000 33

 13 omega   77.00  105.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   77.0000    0.0000 28

 14 omega   30.00   67.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   60.0000 37

 15 omega  -66.00   27.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756   57.0000  -30.0000 93

 16 omega    4.00   78.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000 -180.0000 74

 17 omega   66.00   95.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000   90.0000 29

 18 omega  -67.00  -16.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000  150.0000 51

 19 omega -161.00 -131.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -30.0000  -30.0000 30

 20 omega  126.00  154.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000 -180.0000 28

 21 omega  105.00  156.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   15.0000    0.0000 51

 22 omega   30.00   62.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -90.0000 32

 23 omega   49.00   98.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   15.0000    0.0000 49

 24 omega   39.00   67.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   30.0000 28

 25 omega   96.00  156.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000   60.0000 60

 26 omega   34.00   59.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000 -150.0000 25

 27 omega   58.00  103.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000    0.0000 45

 28 omega   54.00  109.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000 -180.0000 55

 29 omega   78.00  106.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   77.0000   90.0000 28

 30 omega   57.00  117.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000 -180.0000 60

 31 omega   35.00  139.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000 -180.0000 104

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0190879
_diffrn_orient_matrix_UB_12      -0.0345754
_diffrn_orient_matrix_UB_13      0.0590127
_diffrn_orient_matrix_UB_21      0.0121641
_diffrn_orient_matrix_UB_22      -0.0643737
_diffrn_orient_matrix_UB_23      -0.0328895
_diffrn_orient_matrix_UB_31      0.1160986
_diffrn_orient_matrix_UB_32      0.0123859
_diffrn_orient_matrix_UB_33      -0.0062886
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2491
_diffrn_reflns_av_unetI/netI     0.227
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            50527
_diffrn_reflns_theta_full        71.48
_diffrn_reflns_theta_max         71.48
_diffrn_reflns_theta_min         2.88
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.937
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.36813
_exptl_absorpt_correction_type   multi-scan
_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)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2600
_exptl_crystal_size_max          0.416
_exptl_crystal_size_mid          0.024
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.541
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.09
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (100%).
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 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=0.01(3), 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   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.976
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     777
_refine_ls_number_reflns         11955
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      0.976
_refine_ls_R_factor_all          0.1652
_refine_ls_R_factor_gt           0.0899
_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^)+(0.0332P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1732
_refine_ls_wR_factor_ref         0.2159
_reflns_number_gt                6344
_reflns_number_total             11955
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo5b01418_si_004.cif
_cod_data_source_block           a2013019
_cod_depositor_comments
;

2020-08-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C31 H28 N2 O5 S2), C6 H14'
_cod_original_formula_sum        'C68 H70 N4 O10 S4'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     1231.56
_cod_database_code               4036289