Palladium-catalysed asymmetric allylic alkylation of hydantoins using bench-stable chiral palladium precatalysts.
Clark, Paul; Keenan, Thomas; Liu, Shiqi; Huang, Jingjun; Ma, Yao-Rui; Hasija, Avantika; Huang, Pei-Qiang; Jean, Alexandre; Leitch, David C.; Arseniyadis, Stellios; Chemical communications (Cambridge, England) 61 (2025) 19064–19067; doi:10.1039/d5cc05328e

data_7135108
_publ_section_title
;
 Palladium-catalysed asymmetric allylic alkylation of hydantoins using
 bench-stable chiral palladium precatalysts.
;
_journal_issue                   96
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              19064
_journal_page_last               19067
_journal_paper_doi               10.1039/d5cc05328e
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C23 H25 Cl N2 O2'
_chemical_formula_sum            'C23 H25 Cl N2 O2'
_chemical_formula_weight         396.90
_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     dual
_audit_creation_date             2024-10-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-15 deposited with the CCDC.	2025-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5633(2)
_cell_length_b                   10.5879(2)
_cell_length_c                   18.4454(4)
_cell_measurement_reflns_used    13602
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.7700
_cell_measurement_theta_min      4.7830
_cell_volume                     2062.99(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_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     74.00 100.00   0.50    0.50    --   43.40  55.00  90.00   52
  2  \w      1.00  27.00   0.50    0.50    --   43.40  55.00  90.00   52
  3  \w    -44.00 -18.00   0.50    0.50    --   43.40  55.00  90.00   52
  4  \w    -46.00  -7.00   0.50    0.50    --   43.40  55.00 120.00   78
  5  \w     95.00 123.00   0.50    0.50    --   43.40  55.00-180.00   56
  6  \w     21.00  47.00   0.50    0.50    --   43.40  55.00-180.00   52
  7  \w    -45.00 -14.00   0.50    0.50    --   43.40  55.00-180.00   62
  8  \w     55.00  85.00   0.50    0.50    --   43.40  55.00-180.00   60
  9  \w    -39.00 135.00   0.50    0.50    --   46.00  55.00 150.00  348
 10  \w    -43.00 133.00   0.50    0.50    --   46.00  55.00-120.00  352
 11  \w    -41.00   6.00   0.50    0.50    --   46.00  55.00-150.00   94
 12  \w     19.00  81.00   0.50    0.50    --  108.20  55.00  60.00  124
 13  \w     93.00 124.00   0.50    0.50    --  108.20  55.00  90.00   62
 14  \w     19.00  64.00   0.50    0.50    --  108.20  55.00 120.00   90
 15  \w     19.00  66.00   0.50    0.50    --  108.20  55.00 -60.00   94
 16  \w     19.00 196.00   0.50    0.50    --  108.20  55.00 -90.00  354
 17  \w     55.00  90.00   0.50    0.50    --  108.20  55.00  90.00   70
 18  \w     62.00 119.00   0.50    0.50    --  108.20  55.00 150.00  114
 19  \w     19.00  59.00   0.50    0.50    --  108.20  55.00 150.00   80
 20  \w     19.00  45.00   0.50    0.50    --  108.20  55.00  90.00   52
 21  \w     22.00  59.00   0.50    0.50    --  108.20  55.00   0.00   74
 22  \w     65.00 134.00   0.50    0.50    --  108.20  55.00   0.00  138
 23  \w    145.00 170.00   0.50    0.50    --  108.20  55.00-120.00   50
 24  \w    132.00 158.00   0.50    0.50    --  108.20  55.00-150.00   52
 25  \w     19.00  91.00   0.50    0.50    --  108.20  55.00-120.00  144
 26  \w     19.00 178.00   0.50    0.50    --  108.20  55.00  30.00  318
 27  \w     30.00 167.00   0.50    0.50    --  108.20  55.00 -30.00  274
 28  \w     19.00  45.00   0.50    0.50    --  108.20  55.00-180.00   52
 29  \w     19.00  69.00   0.50    0.50    --  108.20  55.00-150.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RINC): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0137189000
_diffrn_orient_matrix_UB_12      0.0613884000
_diffrn_orient_matrix_UB_13      0.0752814000
_diffrn_orient_matrix_UB_21      0.0104449000
_diffrn_orient_matrix_UB_22      -0.1310138000
_diffrn_orient_matrix_UB_23      0.0358399000
_diffrn_orient_matrix_UB_31      0.1448723000
_diffrn_orient_matrix_UB_32      0.0152541000
_diffrn_orient_matrix_UB_33      0.0045064000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            23337
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.491
_diffrn_reflns_theta_min         4.795
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    1.799
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.824
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.141
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1673 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         4190
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0404P)^2^+0.3062P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0696
_refine_ls_wR_factor_ref         0.0702
_reflns_Friedel_coverage         0.752
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4052
_reflns_number_total             4190
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05328e2.cif
_cod_data_source_block           s6594l
_cod_depositor_comments          'Adding full bibliography for 7135108.cif.'
_cod_database_code               7135108
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C23H25ClN2O2
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.800
_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:
 C17(H17A,H17B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C2(H2), C16(H16), C18(H18), C6(H6), C12(H12), C13(H13),
 C15(H15), C14(H14)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              51132
_shelx_hkl_checksum              83824
_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 1.722
_oxdiff_exptl_absorpt_empirical_full_min 0.644