Carbene-catalyzed enantioselective construction of a quasi-symmetrical spirocyclic hydroquinone with a minor chiral distinction
Ren, Panlong; Zhao, Qing; Chi, Yonggui Robin; Zhu, Tingshun; Chemical Science 16 (2025) 8940–8945; doi:10.1039/D5SC01605C

data_1575022
_publ_section_title
;
 Carbene-catalyzed enantioselective construction of a quasi-symmetrical
 spirocyclic hydroquinone with a minor chiral distinction
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              8940
_journal_page_last               8945
_journal_paper_doi               10.1039/D5SC01605C
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C24 H19 Cl O5)'
_chemical_formula_sum            'C48 H38 Cl2 O10'
_chemical_formula_weight         845.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-10-30 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.3060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.27670(10)
_cell_length_b                   7.84770(10)
_cell_length_c                   19.7078(2)
_cell_measurement_reflns_used    8826
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      73.6110
_cell_measurement_theta_min      3.4660
_cell_volume                     1937.92(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'Pilatus3R 200K-A'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.965
_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    -24.00  20.00   0.50    0.50    --    0.00 -57.00-120.00   88
  2  \w    -15.00  28.00   0.50    0.50    --    0.00 -82.00-150.00   86
  3  \w    -60.00 -33.00   0.50    0.50    --    0.00 -57.00-120.00   54
  4  \w    -31.00  25.00   0.50    0.50    --    0.00 -82.00 120.00  112
  5  \w     90.00 184.00   0.50    2.50    --   94.60  82.00   0.00  188
  6  \w    129.00 155.00   0.50    2.50    --   94.60  82.00 150.00   52
  7  \w      6.00 124.00   0.50    2.50    --   94.60 -77.00  60.00  236
  8  \w     75.00 184.00   0.50    2.50    --   94.60  45.00 -60.00  218
  9  \w     94.00 120.00   0.50    2.50    --   94.60 -82.00 -60.00   52
 10  \w    101.00 127.00   0.50    2.50    --   94.60  82.00 150.00   52
 11  \w     22.00 118.00   0.50    2.50    --   94.60 -15.00 120.00  192
 12  \w      5.00  90.00   0.50    2.50    --   94.60 -61.00  60.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1105705000
_diffrn_orient_matrix_UB_12      -0.0848208000
_diffrn_orient_matrix_UB_13      -0.0299582000
_diffrn_orient_matrix_UB_21      0.0238421000
_diffrn_orient_matrix_UB_22      -0.0501103000
_diffrn_orient_matrix_UB_23      -0.0687059000
_diffrn_orient_matrix_UB_31      0.0481896000
_diffrn_orient_matrix_UB_32      -0.1698096000
_diffrn_orient_matrix_UB_33      0.0352906000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11009
_diffrn_reflns_point_group_measured_fraction_full 0.800
_diffrn_reflns_point_group_measured_fraction_max 0.758
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.022
_diffrn_reflns_theta_min         2.375
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'MicroMax 007 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.050
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93215
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 1746 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.042(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         5987
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0310
_refine_ls_R_factor_gt           0.0297
_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^)+(0.0499P)^2^+0.0199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.458
_reflns_Friedel_fraction_full    0.565
_reflns_Friedel_fraction_max     0.515
_reflns_number_gt                5713
_reflns_number_total             5987
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01605c2.cif
_cod_data_source_block           wk13ome
_cod_database_code               1575022
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C94 H76 Cl4 N2 O20 '
_shelx_estimated_absorpt_t_max   0.837
_shelx_estimated_absorpt_t_min   0.791
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C15(H15A,H15B), C51(H51A,H51B), C14(H14A,H14B), C50(H50A,H50B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C6(H6), C36(H36), C19(H19), C7(H7), C39(H39), C48(H48), C18(H18),
 C17(H17), C46(H46), C47(H47), C37(H37)
2.c Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C23(H23A,H23B,H23C), C30(H30A,H30B,
 H30C), C26(H26A,H26B,H26C), C53(H53A,H53B,H53C)
;
_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 1.131
_oxdiff_exptl_absorpt_empirical_full_min 0.901