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_1575021
_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         'C27 H20 F N O6'
_chemical_formula_sum            'C27 H20 F N O6'
_chemical_formula_weight         473.44
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-09-13 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                95.0280(10)
_cell_angle_beta                 94.3680(10)
_cell_angle_gamma                92.2160(10)
_cell_formula_units_Z            4
_cell_length_a                   7.79410(10)
_cell_length_b                   15.0015(2)
_cell_length_c                   18.74620(10)
_cell_measurement_reflns_used    24487
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      74.1260
_cell_measurement_theta_min      2.9810
_cell_volume                     2174.82(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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Pilatus3R 200K-A'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.973
_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    -30.00  31.00   0.50    1.16    --    0.00 -82.00-120.00  122
  2  \w    -49.00  51.00   0.50    1.16    --   32.00 -48.00  30.91  200
  3  \w     85.00 124.00   0.50    1.16    --   36.00  72.00 -57.55   78
  4  \w     10.00  37.00   0.50    1.16    --   36.00  72.00 -57.55   54
  5  \w     68.00 125.00   0.50    1.16    --   40.00  72.00  78.80  114
  6  \w     14.00  46.00   0.50    1.16    --   40.00  72.00  78.80   64
  7  \w     28.00  54.00   0.50    1.80    --   48.00  73.00  -1.34   52
  8  \w     28.00  60.00   0.50    1.80    --   52.00  73.00-151.66   64
  9  \w     31.00  65.00   0.50    1.80    --   56.00  74.00  39.78   68
 10  \w     32.00  58.00   0.50    1.80    --   56.00  75.00 -93.96   52
 11  \w     30.00  59.00   0.50    1.80    --   56.00  73.00 157.14   58
 12  \w     32.00  60.00   0.50    1.80    --   60.00  75.00 107.25   56
 13  \w     32.00  60.00   0.50    1.80    --   60.00  75.00  76.38   56
 14  \w    114.00 140.00   0.50    1.80    --   60.00  75.00  76.38   52
 15  \w     32.00  58.00   0.50    1.80    --   60.00  75.00 -63.78   52
 16  \w     36.00  66.00   0.50    1.80    --   64.00  75.00-147.11   60
 17  \w     40.00  67.00   0.50    1.80    --   68.00  75.00 140.48   54
 18  \w     41.00  67.00   0.50    1.80    --   68.00  75.00 -52.10   52
 19  \w     46.00  72.00   0.50    1.80    --   72.00  69.00-102.62   52
 20  \w     44.00  93.00   0.50    1.80    --   72.00  75.00 -22.27   98
 21  \w     88.00 114.00   0.50    1.80    --   72.00  69.00-102.62   52
 22  \w     45.00  84.00   0.50    1.80    --   72.00  74.00  60.74   78
 23  \w    137.00 163.00   0.50    1.80    --   76.00  74.00  22.82   52
 24  \w     48.00  74.00   0.50    1.80    --   76.00  74.00  22.82   52
 25  \w     48.00  74.00   0.50    1.80    --   76.00  75.00 170.18   52
 26  \w     50.00  83.00   0.50    1.80    --   76.00  72.00-153.78   66
 27  \w    130.00 166.00   0.50    1.80    --   80.00  65.00 -43.77   72
 28  \w     56.00 102.00   0.50    1.80    --   80.00  65.00 -43.77   92
 29  \w     56.00  82.00   0.50    1.80    --   80.00  64.00 112.80   52
 30  \w     57.00  84.00   0.50    1.80    --   80.00  62.00 -70.10   54
 31  \w     58.00  89.00   0.50    1.80    --   84.00  70.00  74.22   62
 32  \w    101.00 172.00   0.50    1.80    --   84.00  70.00  74.22  142
 33  \w    145.00 177.00   0.50    1.80    --   88.00  69.00  39.80   64
 34  \w     63.00 142.00   0.50    1.80    --   88.00  69.00  39.80  158
 35  \w      6.00  82.00   0.50    1.80    --   95.80 -82.00  90.00  152
 36  \w     71.00 119.00   0.50    1.80    --   95.80  67.00 134.68   96
 37  \w      6.00 127.00   0.50    1.80    --   95.80 -82.00 -30.00  242
 38  \w     40.00 108.00   0.50    1.80    --   95.80 -82.00 150.00  136
 39  \w    146.00 184.00   0.50    1.80    --   95.80  60.00 104.57   76
 40  \w     71.00 178.00   0.50    1.80    --   95.80  63.00 -74.22  214
 41  \w     75.00 129.00   0.50    1.80    --   95.80  60.00 104.57  108
 42  \w     71.00 184.00   0.50    1.80    --   95.80  68.00 170.35  226
 43  \w     75.00 121.00   0.50    1.80    --   95.80  61.00-150.00   92
 44  \w     73.00 185.00   0.50    1.80    --   95.80  58.00  23.65  224
 45  \w     76.00 185.00   0.50    1.80    --   95.80  58.00 -47.63  218
 46  \w     35.00 126.00   0.50    1.80    --   95.80 -82.00  60.00  182
 47  \w    117.00 180.00   0.50    1.80    --   95.80  71.00 -27.07  126
 48  \w     70.00 131.00   0.50    1.80    --   95.80  67.00 118.71  122
 49  \w      8.00  34.00   0.50    1.80    --   95.80 -82.00  60.00   52
 50  \w     72.00 184.00   0.50    1.80    --   95.80  59.00-126.26  224
 51  \w     68.00 101.00   0.50    1.80    --   95.80  71.00 -27.07   66
 52  \w     55.00 123.00   0.50    1.80    --   95.80 -82.00-120.00  136
 53  \w     22.00  48.00   0.50    1.80    --   95.80 -82.00-120.00   52
 54  \w     69.00 182.00   0.50    1.80    --   95.80  72.00 152.64  226
 55  \w     96.00 126.00   0.50    1.80    --   95.80 -82.00 -90.00   60
 56  \w     69.00 184.00   0.50    1.80    --   95.80  75.00-127.79  230
 57  \w     39.00  90.00   0.50    1.80    --   95.80 -82.00 -90.00  102
 58  \w     91.00 117.00   0.50    1.80    --   95.80 -82.00  90.00   52
 59  \w    136.00 162.00   0.50    1.80    --   95.80  67.00 134.68   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'MicroMax 007 (Cu) X-ray Source'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0330977000
_diffrn_orient_matrix_UB_12      -0.0971380000
_diffrn_orient_matrix_UB_13      0.0179486000
_diffrn_orient_matrix_UB_21      -0.0476807000
_diffrn_orient_matrix_UB_22      -0.0290075000
_diffrn_orient_matrix_UB_23      -0.0801593000
_diffrn_orient_matrix_UB_31      0.1897626000
_diffrn_orient_matrix_UB_32      -0.0193038000
_diffrn_orient_matrix_UB_33      -0.0100946000
_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  0.0453
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            51424
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.411
_diffrn_reflns_theta_min         2.960
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Pilatus3R 200K-A'
_exptl_absorpt_coefficient_mu    0.908
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62255
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       needle
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.769
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 6395 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1280
_refine_ls_number_reflns         16487
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0901P)^2^+0.1431P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1301
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.906
_reflns_Friedel_fraction_full    0.946
_reflns_Friedel_fraction_max     0.882
_reflns_number_gt                14980
_reflns_number_total             16487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01605c2.cif
_cod_data_source_block           a74_collect
_cod_database_code               1575021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C114 H94 F4 N6 O20 '
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.685
_reflns_odcompleteness_completeness 99.55
_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, All O(H) groups
2.a Riding coordinates:
 C27C(H27D,H27E,H27F)
2.b Secondary CH2 refined with riding coordinates:
 C15B(H15E,H15F), C14B(H14E,H14F), C15C(H15C,H15D), C14A(H14A,H14B), C14C(H14C,
 H14D), C15A(H15A,H15B), C14(H14G,H14H), C15(H15G,H15H)
2.c Aromatic/amide H refined with riding coordinates:
 C21B(H21B), C1B(H1BA), C4B(H4B), C21(H21), C22C(H22C), C4C(H4C), C1C(H1CA),
 C22A(H22A), C1A(H1AA), C4A(H4A), C1(H1D), C4(H4), C22B(H22B), C2B(H2BA),
 C21A(H21A), C21C(H21C), C2C(H2CA), C2A(H2AA), C22(H22), C2(H2D)
2.d Idealised Me refined as rotating group:
 C27A(H27A,H27B,H27C), C27B(H27G,H27H,H27I), C26B(H26G,H26H,H26I), C26A(H26A,
 H26B,H26C), C26C(H26D,H26E,H26F), C27(H27J,H27K,H27L), C25C(H25D,H25E,H25F),
 C25B(H25G,H25H,H25I), C25A(H25A,H25B,H25C), C26(H26J,H26K,H26L), C25(H25J,H25K,
 H25L)
2.e Idealised tetrahedral OH refined as rotating group:
 O1A(H1A), O1B(H1B), O2B(H2B), O2(H2), O2C(H2C), O1(H1), O2A(H2A), O1C(H1C)
;
_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 1.420
_oxdiff_exptl_absorpt_empirical_full_min 0.665