Palladium-catalyzed enantioselective decarboxylative [3+2] cycloaddition of 5‑vinyloxazolidine-2,4-diones with sterically encumbered ketoimines toward chiral polycyclic 1,4-imidazolidinones
Liao, Juan; Sun, Wei; Sun, Guo-Yin; Peng, Xue-Song; Yang, Lei; You, Yong; Wang, Zhen-Hua; Zhao, Jian-Qiang; Zhou, Ming-Qiang; Yuan, Wei-Cheng; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D6OB00235H

data_7161090
_publ_section_title
;
 Palladium-catalyzed enantioselective decarboxylative [3 + 2]
 cycloaddition of 5-vinyloxazolidine-2,4-diones with sterically encumbered
 ketoimines toward chiral polycyclic 1,4-imidazolidinones.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3192
_journal_page_last               3197
_journal_paper_doi               10.1039/d6ob00235h
_journal_volume                  24
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H24 N2 O6 S'
_chemical_formula_sum            'C27 H24 N2 O6 S'
_chemical_formula_weight         504.54
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2023-12-29
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-09-03 deposited with the CCDC.	2026-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.96870(10)
_cell_length_b                   13.38660(10)
_cell_length_c                   13.91060(10)
_cell_measurement_reflns_used    14425
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.5390
_cell_measurement_theta_min      3.1770
_cell_volume                     2414.97(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.980
_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    -17.00  28.00   0.50    0.20    --   48.01 -42.00 101.00   90
  2  \w     38.00  64.00   0.50    0.40    --  104.75 -57.00 120.00   52
  3  \w     33.00  58.00   0.50    0.40    --  104.75 -57.00  60.00   50
  4  \w    -24.00  20.00   0.50    0.20    --   48.01 -19.00 -30.00   88
  5  \w     33.00  68.00   0.50    0.40    --  104.75 -57.00 -30.00   70
  6  \w     38.00 115.00   0.50    0.40    --  104.75 -85.00 -94.00  154
  7  \w     94.00 164.00   0.50    0.40    --  104.75  42.00-107.00  140
  8  \w    147.00 173.00   0.50    0.40    --  104.75  19.00 -60.00   52
  9  \w     97.00 137.00   0.50    0.40    --  104.75  19.00 -60.00   80
 10  \w     45.00  95.00   0.50    0.40    --  104.75 -99.00  30.00  100
 11  \w     38.00 111.00   0.50    0.40    --  104.75-125.00-150.00  146
 12  \w    -24.00  13.00   0.50    0.20    --  -48.01  19.00 -60.00   74
 13  \w    -59.00 -33.00   0.50    0.40    -- -104.00  57.00-150.00   52
 14  \w    -61.00 -34.00   0.50    0.40    -- -104.00  57.00 -90.00   54
 15  \w    -44.00  14.00   0.50    0.20    --  -48.01  42.00-107.00  116
 16  \w    -61.00 -33.00   0.50    0.40    -- -104.00  57.00 -30.00   56
 17  \w    -63.00 -32.00   0.50    0.40    -- -104.00  57.00   0.00   62
 18  \w    -63.00 -38.00   0.50    0.40    -- -104.00  57.00  90.00   50
 19  \w    -76.00 -35.00   0.50    0.20    --  -48.01 125.00  60.00   82
 20  \w   -106.00 -53.00   0.50    0.40    -- -104.00 106.00 112.00  106
 21  \w   -124.00 -90.00   0.50    0.40    -- -104.00 -57.00  60.00   68
 22  \w   -172.00-142.00   0.50    0.40    -- -104.00 -57.00  60.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0529227000
_diffrn_orient_matrix_UB_12      -0.0832422000
_diffrn_orient_matrix_UB_13      -0.0586158000
_diffrn_orient_matrix_UB_21      -0.1022522000
_diffrn_orient_matrix_UB_22      0.0584198000
_diffrn_orient_matrix_UB_23      0.0033893000
_diffrn_orient_matrix_UB_31      0.0291457000
_diffrn_orient_matrix_UB_32      0.0539649000
_diffrn_orient_matrix_UB_33      -0.0938765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_av_unetI/netI     0.0135
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14863
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.508
_diffrn_reflns_theta_min         4.584
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.587
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light colourless'
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2058 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(4)
_refine_ls_extinction_coef       0.0190(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4883
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0234
_refine_ls_R_factor_gt           0.0234
_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^)+(0.0365P)^2^+0.4861P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0612
_refine_ls_wR_factor_ref         0.0613
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.938
_reflns_number_gt                4873
_reflns_number_total             4883
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00235h2.cif
_cod_data_source_block           1225lj-1
_cod_depositor_comments
'Adding full bibliography for 7161089--7161090.cif.'
_cod_database_code               7161090
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C29(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C)
;
_shelx_res_checksum              11946
_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 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.735