Organocatalytic asymmetric synthesis of oxazolidino spiropyrazolinones <i>via N</i>,<i>O</i>-acetalization/aza Michael addition domino reaction between <i>N</i>-Boc pyrazolinone ketimines and γ-hydroxyenones.
Gil-Ordóñez, Marta; Martín, Laura; Maestro, Alicia; Andrés, José M; Organic & biomolecular chemistry 21 (2023) 2361–2369; doi:10.1039/d2ob02290g

data_7159166
_publ_section_title
;
 Organocatalytic asymmetric synthesis of oxazolidino spiropyrazolinones
 <i>via N</i>,<i>O</i>-acetalization/aza Michael addition domino reaction
 between <i>N</i>-Boc pyrazolinone ketimines and &#x3b3;-hydroxyenones.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2361
_journal_page_last               2369
_journal_paper_doi               10.1039/d2ob02290g
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H28 Cl N3 O5'
_chemical_formula_sum            'C30 H28 Cl N3 O5'
_chemical_formula_weight         546.00
_chemical_name_systematic
'tert-butyl (3R,5S)-3-(2-(4-chlorophenyl)-2-oxoethyl)-9-oxo-6,8-diphenyl-1-oxa-4,7,8-triazaspiro[4.4]non-6-ene-4-carboxylate'
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-29 deposited with the CCDC.	2023-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3506(2)
_cell_length_b                   11.0548(3)
_cell_length_c                   35.8931(9)
_cell_measurement_reflns_used    11071
_cell_measurement_temperature    298
_cell_measurement_theta_max      75.0250
_cell_measurement_theta_min      3.8370
_cell_volume                     3313.44(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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   -128.00 -34.00   1.00    1.13    --  -41.06 178.00  90.00   94
  2  \w   -116.00 -17.00   1.00    1.13    --  -41.06 -37.00-180.00   99
  3  \w     27.00 110.00   1.00    4.51    --  110.01 -94.00-150.00   83
  4  \w     84.00 178.00   1.00    4.51    --  110.01  45.00 -30.00   94
  5  \w     99.00 178.00   1.00    4.51    --  110.01  87.00-102.00   79
  6  \w     38.00 139.00   1.00    4.51    --  110.01 -61.00-120.00  101
  7  \w   -117.00  -8.00   1.00    1.13    --  -41.06 -77.00  90.00  109
  8  \w   -113.00 -13.00   1.00    1.13    --  -41.06 -57.00 -60.00  100
  9  \w     57.00 178.00   1.00    4.51    --  110.01  15.00 120.00  121
 10  \w     37.00 118.00   1.00    4.51    --  110.01-125.00  90.00   81
 11  \w     79.00 178.00   1.00    4.51    --  110.01  69.00  18.00   99
 12  \w     81.00 178.00   1.00    4.51    --  110.01  61.00-150.00   97
 13  \w   -117.00  -8.00   1.00    1.13    --  -41.06 -77.00-180.00  109
 14  \w     57.00 130.00   1.00    1.13    --   41.06 178.00 120.00   73
 15  \w     80.00 178.00   1.00    4.51    --  110.01  67.00 151.00   98
 16  \w     27.00  58.00   1.00    4.51    --  110.01 -94.00 120.00   31
 17  \w     84.00 178.00   1.00    4.51    --  110.01  45.00 -90.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0099371000
_diffrn_orient_matrix_UB_12      -0.0748826000
_diffrn_orient_matrix_UB_13      -0.0361251000
_diffrn_orient_matrix_UB_21      -0.1399325000
_diffrn_orient_matrix_UB_22      0.0794994000
_diffrn_orient_matrix_UB_23      -0.0135491000
_diffrn_orient_matrix_UB_31      0.1198370000
_diffrn_orient_matrix_UB_32      0.0864970000
_diffrn_orient_matrix_UB_33      -0.0188236000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            26672
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.313
_diffrn_reflns_theta_min         4.185
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.327
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.257
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.095
_exptl_crystal_description       prism
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.737
_exptl_crystal_size_mid          0.372
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.158
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 1907 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.012(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         6729
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0895P)^2^+0.0947P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1406
_refine_ls_wR_factor_ref         0.1560
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                5535
_reflns_number_total             6729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob02290g2.cif
_cod_data_source_block           gm-mg-1298-1
_cod_depositor_comments          'Adding full bibliography for 7159166.cif.'
_cod_database_code               7159166
_shelx_shelxl_version_number     2014/7
_publ_section_exptl
;
Any special experimental details
;
_chemical_oxdiff_formula         'C30 H29 N4 O5 Cl'
_chemical_oxdiff_usercomment     'Colorless block'
_shelx_estimated_absorpt_t_max   0.692
_shelx_estimated_absorpt_t_min   0.441
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C00F(H00F)
1.b Secondary CH2 refined with riding coordinates:
 C00J(H00A,H00B), C00K(H00C,H00D)
1.c Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q),
 C00S(H00S), C00T(H00T), C00U(H00U), C00X(H00X), C00Y(H00Y), C010(H010),
 C012(H012), C013(H013)
1.d Idealised Me refined as rotating group:
 C00W(H00E,H00H,H00I), C00Z(H00J,H00K,H00L), C011(H01A,H01B,H01C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              75092
_shelx_fab_checksum              57648
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.949
_oxdiff_exptl_absorpt_empirical_full_min 0.470