Constructing chiral bicyclo[3.2.1]octanes <i>via</i> low-loading organocatalysis.
Ashok, Etikala; Lakshmi, Pandhiti R.; Sravanthi, Revoju; Ramachary, Dhevalapally B.; Organic & biomolecular chemistry 23 (2025) 5616–5628; doi:10.1039/d5ob00203f

data_7160517
_publ_section_title
;
 Constructing chiral bicyclo[3.2.1]octanes <i>via</i> low-loading
 organocatalysis.
;
_journal_issue                   23
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5616
_journal_page_last               5628
_journal_paper_doi               10.1039/d5ob00203f
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C21 H22 Br N O6'
_chemical_formula_sum            'C21 H22 Br N O6'
_chemical_formula_weight         464.30
_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     dual
_audit_creation_date             2023-09-08
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_audit_update_record
;
2024-06-04 deposited with the CCDC.	2025-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0203(7)
_cell_length_b                   10.9547(10)
_cell_length_c                   28.092(3)
_cell_measurement_reflns_used    5366
_cell_measurement_temperature    234
_cell_measurement_theta_max      26.4770
_cell_measurement_theta_min      2.3390
_cell_volume                     2160.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      234
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.949
_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    -54.00  74.00   0.50   17.75    --   16.22 -15.00 -90.00  256
  2  \w    -87.00 -36.00   0.50   17.75    --  -15.60 158.00-144.00  102
  3  \w     32.00  75.00   0.50   17.75    --   16.22-134.00  74.00   86
  4  \w    -25.00  15.00   0.50   17.75    --   16.22 -10.00 111.00   80
  5  \w      6.00  35.00   0.50   17.75    --  -15.60  77.00 150.00   58
  6  \w    -45.00 -20.00   0.50   17.75    --  -15.60  77.00 150.00   50
  7  \w    -79.00   9.00   0.50   17.75    --  -15.60 -61.00 120.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0185391000
_diffrn_orient_matrix_UB_12      -0.0601146000
_diffrn_orient_matrix_UB_13      0.0080410000
_diffrn_orient_matrix_UB_21      0.0066311000
_diffrn_orient_matrix_UB_22      -0.0201807000
_diffrn_orient_matrix_UB_23      -0.0239741000
_diffrn_orient_matrix_UB_31      0.0990083000
_diffrn_orient_matrix_UB_32      0.0129109000
_diffrn_orient_matrix_UB_33      0.0000947000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0578
_diffrn_reflns_av_unetI/netI     0.0927
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            11339
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.211
_diffrn_reflns_theta_min         2.358
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic orangish orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.158
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 698 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4479
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1066
_refine_ls_R_factor_gt           0.0605
_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^)+(0.0394P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.910
_reflns_number_gt                2591
_reflns_number_total             4479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00203f4.cif
_cod_data_source_block           dbr64
_cod_depositor_comments
'Adding full bibliography for 7160515--7160517.cif.'
_cod_database_code               7160517
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Br'
_shelx_estimated_absorpt_t_max   0.749
_shelx_estimated_absorpt_t_min   0.723
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C4(H4), C13(H13), C15(H15), C14(H14)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C17(H17A,H17B,H17C), C20(H20A,H20B,H20C), C19(H19A,H19B,
 H19C)
;
_shelx_res_checksum              75964
_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 1.877
_oxdiff_exptl_absorpt_empirical_full_min 0.593