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_1575023
_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_formula_moiety         '2(C24 H19 Br O5)'
_chemical_formula_sum            'C48 H38 Br2 O10'
_chemical_formula_weight         934.60
_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                 108.449(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.3142(2)
_cell_length_b                   7.83960(10)
_cell_length_c                   19.8412(3)
_cell_measurement_reflns_used    9737
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      73.4640
_cell_measurement_theta_min      3.5200
_cell_volume                     1964.55(5)
_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      100.0(4)
_diffrn_detector                 'Pilatus3R 200K-A'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_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    -32.00  24.00   0.50    0.50    --    0.00 -82.00   0.00  112
  2  \w    -17.00  29.00   0.50    0.50    --    0.00 -82.00  90.00   92
  3  \w    -26.00  14.00   0.50    0.50    --    0.00 -82.00-150.00   80
  4  \w    -26.00  10.00   0.50    0.50    --    0.00 -82.00 -90.00   72
  5  \w    154.00 183.00   0.50    1.00    --   94.60  82.00  60.00   58
  6  \w     77.00 170.00   0.50    1.00    --   94.60  45.00 -30.00  186
  7  \w     84.00 109.00   0.50    1.00    --   94.60 -30.00-180.00   50
  8  \w     24.00 104.00   0.50    1.00    --   94.60 -61.00-180.00  160
  9  \w     11.00  99.00   0.50    1.00    --   94.60 -15.00-180.00  176
 10  \w      6.00  32.00   0.50    1.00    --   94.60 -30.00-180.00   52
 11  \w      5.00 124.00   0.50    1.00    --   94.60 -77.00-180.00  238
 12  \w     13.00 120.00   0.50    1.00    --   94.60   0.00   0.00  214
;
_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      -0.0300829000
_diffrn_orient_matrix_UB_12      0.1062999000
_diffrn_orient_matrix_UB_13      0.0560508000
_diffrn_orient_matrix_UB_21      0.0630771000
_diffrn_orient_matrix_UB_22      0.1524184000
_diffrn_orient_matrix_UB_23      -0.0148301000
_diffrn_orient_matrix_UB_31      -0.0999468000
_diffrn_orient_matrix_UB_32      0.0637431000
_diffrn_orient_matrix_UB_33      -0.0578177000
_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  0.0231
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_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       15
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11123
_diffrn_reflns_point_group_measured_fraction_full 0.811
_diffrn_reflns_point_group_measured_fraction_max 0.776
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.709
_diffrn_reflns_theta_min         2.347
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'MicroMax 007 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72275
_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    1.580
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.172
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 1927 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.013(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         6177
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0356
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0630P)^2^+1.4457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0943
_refine_ls_wR_factor_ref         0.0947
_reflns_Friedel_coverage         0.477
_reflns_Friedel_fraction_full    0.590
_reflns_Friedel_fraction_max     0.543
_reflns_number_gt                6069
_reflns_number_total             6177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01605c2.cif
_cod_data_source_block           wk13
_cod_database_code               1575023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C94 H78 Br4 N4 O18 '
_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:
 C51(H51A,H51B), C21(H21A,H21B), C50(H50A,H50B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C37(H37), C9(H9), C7(H7), C46(H46), C6(H6), C39(H39), C40(H40), C18(H18),
 C48(H48), C16(H16), C17(H17), C47(H47)
2.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C53(H53A,H53B,H53C), C60(H60A,H60B,H60C), C28(H28A,H28B,
 H28C), C23(H23A,H23B,H23C), C56(H56A,H56B,H56C)
;
_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 1.344
_oxdiff_exptl_absorpt_empirical_full_min 0.848