Highly diastereoselective C → N acyl rearrangement in polysubstituted pyrrolidine 2,2-dicarboxylates. Stereocontrolled synthesis of densely functionalized prolines
Reboredo, Silvia; García-Marijuan, Ainara; Uria, Uxue; Reyes, Efraím; Carrillo, Luisa; Ugarriza, Iratxe; Vicario, Jose L.; Organic Chemistry Frontiers 5 (2018) 933–; doi:10.1039/C7QO00793K

data_1553899
_publ_section_title
;
 Highly diastereoselective C \\rightarrow N acyl rearrangement in
 polysubstituted pyrrolidine 2,2-dicarboxylates. Stereocontrolled
 synthesis of densely functionalized prolines
;
_journal_issue                   6
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              933
_journal_paper_doi               10.1039/C7QO00793K
_journal_volume                  5
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C14 H19 N O3 S'
_chemical_formula_sum            'C14 H19 N O3 S'
_chemical_formula_weight         281.36
_chemical_name_systematic
(2R,4S,5R)-3-(Hydroxymethyl)-8,8-dimethyl-2-(thiophen-2-yl)-7-oxa-1-azaspiro[4.4]nonan-6-one
_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'
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-06T14:10:12-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2017-11-06 deposited with the CCDC.
2017-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.36821(6)
_cell_length_b                   11.71337(15)
_cell_length_c                   21.6232(3)
_cell_measurement_reflns_used    6484
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.766
_cell_measurement_theta_min      4.068
_cell_measurement_wavelength     1.54184
_cell_volume                     1359.66(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_temperature      100.00(10)
_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
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     16.00 110.00   1.00    1.50    --   40.58  57.00 -60.00   94
  2  \w     -6.00  44.00   1.00    1.50    --   40.58 -57.00   0.00   50
  3  \w     25.00  72.00   1.00    2.00    --  108.36 -94.00 -30.00   47
  4  \w     80.00 108.00   1.00    2.00    --  108.36 -94.00 -30.00   28
  5  \w     42.00  68.00   1.00    2.00    --  108.36 -30.00  60.00   26
  6  \w     36.00  61.00   1.00    2.00    --  108.36 -45.00   0.00   25
  7  \w     34.00  71.00   1.00    2.00    --  108.36 -45.00 -30.00   37
  8  \w     25.00 133.00   1.00    2.00    --  108.36 -15.00  90.00  108
  9  \w    -28.00  65.00   1.00    1.50    --   40.58 -57.00 150.00   93
 10  \w      2.00  69.00   1.00    1.50    --   40.58 -57.00  30.00   67
 11  \w      5.00  32.00   1.00    1.50    --   40.58-125.00  30.00   27
 12  \w     35.00  61.00   1.00    2.00    --  108.36 -45.00-180.00   26
 13  \w     90.00 122.00   1.00    2.00    --  108.36-125.00 -60.00   32
 14  \w     40.00  77.00   1.00    2.00    --  108.36 -45.00  30.00   37
 15  \w     39.00  67.00   1.00    2.00    --  108.36-125.00 -60.00   28
 16  \w     77.00 108.00   1.00    2.00    --  108.36 -94.00  30.00   31
 17  \w     30.00 138.00   1.00    2.00    --  108.36 -77.00-180.00  108
 18  \w     35.00  74.00   1.00    2.00    --  108.36 -45.00 -60.00   39
 19  \w     41.00  69.00   1.00    2.00    --  108.36 -30.00  90.00   28
 20  \w     42.00  68.00   1.00    2.00    --  108.36 -45.00   0.00   26
 21  \w     49.00 104.00   1.00    2.00    --  108.36 -94.00 120.00   55
 22  \w     54.00 136.00   1.00    2.00    --  108.36  15.00   0.00   82
 23  \w     88.00 151.00   1.00    2.00    --  108.36   0.00 120.00   63
;
_diffrn_measurement_device       'four-circle\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0546247
_diffrn_orient_matrix_UB_12      -0.0775688
_diffrn_orient_matrix_UB_13      -0.055911
_diffrn_orient_matrix_UB_21      -0.0258032
_diffrn_orient_matrix_UB_22      -0.1032992
_diffrn_orient_matrix_UB_23      0.0436324
_diffrn_orient_matrix_UB_31      -0.2805544
_diffrn_orient_matrix_UB_32      0.0245918
_diffrn_orient_matrix_UB_33      0.0068934
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.038
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            9152
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.998
_diffrn_reflns_theta_min         4.089
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.157
_exptl_absorpt_correction_T_max  0.922
_exptl_absorpt_correction_T_min  0.667
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.349
_exptl_crystal_size_mid          0.239
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.037
_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, 2010).
 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=-0.001(8), 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
Dolomanov, O.V. (2009) OLEX2, J. Appl. Cryst., 42, 339-341. 
Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13.
Spek, A.L. (2009). Acta Cryst. D65, 148-155.
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   -0.005(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2586
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0254
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0264P)^2^+0.4076P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0615
_refine_ls_wR_factor_ref         0.062
_reflns_number_gt                2520
_reflns_number_total             2586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7qo00793k2.cif
_cod_data_source_block           iu706
_cod_database_code               1553899