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_1575827
_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 H15 N3 O'
_chemical_formula_sum            'C21 H15 N3 O'
_chemical_formula_weight         325.36
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2025-05-10
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1974(4)
_cell_length_b                   13.1816(5)
_cell_length_c                   15.5004(6)
_cell_measurement_reflns_used    5487
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.1110
_cell_measurement_theta_min      4.3620
_cell_volume                     1674.89(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (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
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.959
_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      2.00  65.00   0.50    0.08    --   42.49 -78.00 104.00  126
  2  \w     49.00  76.00   0.50    0.10    --  107.57 -78.00 104.00   54
  3  \w     40.00  75.00   0.50    0.10    --  107.57 -77.00 120.00   70
  4  \w    -18.00  60.00   0.50    0.08    --   42.49 -77.00 -90.00  156
  5  \w     37.00  74.00   0.50    0.10    --  107.57 -77.00 -30.00   74
  6  \w     96.00 139.00   0.50    0.10    --  107.57  15.00-150.00   86
  7  \w    112.00 138.00   0.50    0.10    --  107.57  78.00-131.00   52
  8  \w    143.00 175.00   0.50    0.10    --  107.57  78.00-131.00   64
  9  \w    137.00 164.00   0.50    0.10    --  107.57 126.00 -60.00   54
 10  \w     94.00 121.00   0.50    0.10    --  107.57 126.00 -60.00   54
 11  \w     99.00 175.00   0.50    0.10    --  107.57 126.00 150.00  152
 12  \w     59.00  86.00   0.50    0.10    --  107.57 -95.00 150.00   54
 13  \w    -58.00 -32.00   0.50    0.08    --  -42.49  78.00-131.00   52
 14  \w     -5.00  21.00   0.50    0.08    --  -42.49  78.00-131.00   52
 15  \w    -15.00  32.00   0.50    0.08    --  -42.49  38.00 -60.00   94
 16  \w    -13.00  35.00   0.50    0.08    --  -42.49  38.00 -30.00   96
 17  \w     -3.00  34.00   0.50    0.08    --  -42.49  38.00   0.00   74
 18  \w    -73.00 -46.00   0.50    0.10    -- -103.00  78.00-131.00   54
 19  \w    -68.00 -40.00   0.50    0.10    -- -103.00  77.00-150.00   56
 20  \w    -57.00 -29.00   0.50    0.10    -- -103.00  77.00-180.00   56
 21  \w   -121.00 -95.00   0.50    0.10    -- -103.00 -15.00-180.00   52
 22  \w   -125.00 -99.00   0.50    0.10    -- -103.00 -77.00-180.00   52
 23  \w   -160.00-132.00   0.50    0.10    -- -103.00 -77.00-180.00   56
 24  \w   -131.00 -89.00   0.50    0.10    -- -103.00 -15.00 -30.00   84
 25  \w   -174.00-106.00   0.50    0.10    -- -103.00 -78.00 104.00  136
 26  \w   -174.00-100.00   0.50    0.10    -- -103.00 -77.00 150.00  148
 27  \w   -130.00-101.00   0.50    0.10    -- -103.00 -95.00 -60.00   58
 28  \w   -174.00-147.00   0.50    0.10    -- -103.00 -95.00 -60.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1542048000
_diffrn_orient_matrix_UB_12      0.0210936000
_diffrn_orient_matrix_UB_13      0.0539789000
_diffrn_orient_matrix_UB_21      -0.0378524000
_diffrn_orient_matrix_UB_22      -0.0932128000
_diffrn_orient_matrix_UB_23      0.0565141000
_diffrn_orient_matrix_UB_31      0.1005900000
_diffrn_orient_matrix_UB_32      -0.0672910000
_diffrn_orient_matrix_UB_33      -0.0613636000
_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  0.0204
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9558
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.871
_diffrn_reflns_theta_min         4.403
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.650
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74238
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (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    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.563
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 1099 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3178
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0725
_refine_ls_R_factor_gt           0.0686
_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^)+(0.1302P)^2^+0.6030P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.1998
_reflns_Friedel_coverage         0.672
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.873
_reflns_number_gt                2928
_reflns_number_total             3178
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03779d2.cif
_cod_data_source_block           zsm_9_120
_cod_depositor_comments
'Adding full bibliography for 1575826--1575827.cif.'
_cod_original_cell_volume        1674.90(12)
_cod_database_code               1575827
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Cl'
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.915
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C16(H16), C18(H18),
 C19(H19), C20(H20), C21(H21)
;
_shelx_res_checksum              85729
_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 1.523
_oxdiff_exptl_absorpt_empirical_full_min 0.603