Chiral benzo[2.2.1] α-hydroxyketones from a dirhodium(ii)/bisphosphine-catalyzed desymmetrization addition reaction.
Zhan, Shuming; Wang, Chengyu; Duan, Longhui; Gu, Zhenhua; Chemical science 16 (2025) 19397–19402; doi:10.1039/d5sc03779d

data_1575826
_publ_section_title
;
 Chiral benzo[2.2.1] &#x3b1;-hydroxyketones from a
 dirhodium(ii)/bisphosphine-catalyzed desymmetrization addition reaction.
;
_journal_issue                   41
_journal_name_full               'Chemical science'
_journal_page_first              19397
_journal_page_last               19402
_journal_paper_doi               10.1039/d5sc03779d
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H16 O2'
_chemical_formula_sum            'C21 H16 O2'
_chemical_formula_weight         300.34
_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     direct
_audit_creation_date             2024-11-09
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-05-21 deposited with the CCDC.	2025-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.7256(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.13513(12)
_cell_length_b                   6.32967(9)
_cell_length_c                   12.14214(15)
_cell_measurement_reflns_used    7666
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.6090
_cell_measurement_theta_min      5.0360
_cell_volume                     749.788(17)
_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-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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.962
_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     55.00  88.00   0.50    0.05    --   62.21  15.00 120.00   66
  2  \w     74.00 115.00   0.50    0.05    --   75.66  18.00 104.59   82
  3  \w     85.00 110.00   0.50    0.05    --   68.27  24.00  65.95   50
  4  \w     61.00 102.00   0.50    0.05    --   62.21  15.00  60.00   82
  5  \w     55.00  99.00   0.50    0.05    --   62.21  15.00 -60.00   88
  6  \w     61.00 102.00   0.50    0.05    --   62.21  15.00  17.00   82
  7  \w     62.00 101.00   0.50    0.05    --   62.21  15.00 -30.00   78
  8  \w     69.00 109.00   0.50    0.05    --   71.27  15.00  17.00   80
  9  \w     64.00 105.00   0.50    0.05    --   71.27  15.00-120.00   82
 10  \w     68.00  98.00   0.50    0.05    --   68.27  18.00-155.38   60
 11  \w     89.00 115.00   0.50    0.05    --   75.66  20.00-169.93   52
 12  \w     57.00 103.00   0.50    0.05    --   62.21  15.00-180.00   92
 13  \w     75.00 108.00   0.50    0.05    --   74.33  15.00 -90.00   66
 14  \w     71.00 108.00   0.50    0.05    --   74.33  15.00 -30.00   74
 15  \w     67.00  92.00   0.50    0.05    --   74.33  15.00  17.00   50
 16  \w     60.00  86.00   0.50    0.05    --   62.21  15.00 150.00   52
 17  \w     76.00 102.00   0.50    0.05    --   74.33  15.00 150.00   52
 18  \w     67.00 110.00   0.50    0.05    --   71.27  15.00 120.00   86
 19  \w     68.00 104.00   0.50    0.05    --   74.33  15.00  60.00   72
 20  \w     16.00  41.00   0.50    0.05    --    2.00  22.00-172.16   50
 21  \w     43.00  68.00   0.50    0.05    --   30.00  21.00-165.93   50
 22  \w     32.00  58.00   0.50    0.05    --   18.00  22.00-120.97   52
 23  \w     57.00  86.00   0.50    0.05    --   46.00  19.00-170.94   58
 24  \w     52.00  77.00   0.50    0.05    --   38.00  22.00  28.56   50
 25  \w     36.00  64.00   0.50    0.05    --   22.00  21.00 154.97   56
 26  \w     21.00  46.00   0.50    0.05    --    6.00  22.00 175.85   50
 27  \w     21.00  47.00   0.50    0.05    --   22.00-139.00 -48.27   52
 28  \w     25.00  50.00   0.50    0.05    --   62.21-125.00-120.00   50
 29  \w     25.00  78.00   0.50    0.05    --   62.21-125.00-150.00  106
 30  \w     27.00  58.00   0.50    0.05    --   62.21-125.00-180.00   62
 31  \w     26.00  52.00   0.50    0.05    --   62.21-125.00 -30.00   52
 32  \w     29.00  60.00   0.50    0.05    --   62.21-125.00 -90.00   62
 33  \w     25.00  50.00   0.50    0.05    --   62.21-125.00  60.00   50
 34  \w     39.00  68.00   0.50    0.05    --   71.27-125.00  90.00   58
 35  \w     45.00  77.00   0.50    0.05    --   62.21-125.00 120.00   64
 36  \w     64.00  90.00   0.50    0.05    --   74.33-125.00 120.00   52
 37  \w     42.00  77.00   0.50    0.05    --   62.21-125.00 150.00   70
 38  \w     54.00  83.00   0.50    0.05    --   71.27-125.00 120.00   58
 39  \w     42.00  77.00   0.50    0.05    --   74.33-125.00  30.00   70
 40  \w     55.00  90.00   0.50    0.05    --   74.33-125.00 150.00   70
 41  \w     48.00  75.00   0.50    0.05    --   74.33-125.00 -30.00   54
 42  \w     40.00  66.00   0.50    0.05    --   74.33-125.00   0.00   52
 43  \w     38.00  73.00   0.50    0.05    --   74.33-125.00 -90.00   70
 44  \w     41.00  71.00   0.50    0.05    --   74.33-125.00 -60.00   60
 45  \w     39.00  85.00   0.50    0.05    --   71.27-125.00-120.00   92
 46  \w     48.00  90.00   0.50    0.05    --   74.33-125.00-150.00   84
 47  \w     56.00  89.00   0.50    0.05    --   74.33-125.00-180.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0686459000
_diffrn_orient_matrix_UB_12      0.0178225000
_diffrn_orient_matrix_UB_13      -0.0983547000
_diffrn_orient_matrix_UB_21      0.1406457000
_diffrn_orient_matrix_UB_22      -0.0439103000
_diffrn_orient_matrix_UB_23      0.0847205000
_diffrn_orient_matrix_UB_31      -0.0207958000
_diffrn_orient_matrix_UB_32      -0.2387705000
_diffrn_orient_matrix_UB_33      -0.0228962000
_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  0.0340
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9116
_diffrn_reflns_point_group_measured_fraction_full 0.842
_diffrn_reflns_point_group_measured_fraction_max 0.816
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.719
_diffrn_reflns_theta_min         5.057
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.669
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76163
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 846 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2420
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0317
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+0.0920P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0865
_reflns_Friedel_coverage         0.546
_reflns_Friedel_fraction_full    0.676
_reflns_Friedel_fraction_max     0.638
_reflns_number_gt                2402
_reflns_number_total             2420
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03779d2.cif
_cod_data_source_block           8_186
_cod_depositor_comments
'Adding full bibliography for 1575826--1575827.cif.'
_cod_database_code               1575826
_shelx_shelxl_version_number     2018/3
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C13(H13), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21)
2.d Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              90689
_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 2.310
_oxdiff_exptl_absorpt_empirical_full_min 0.706