Enantioselective dearomative formal (3+3) cycloadditions of bicyclobutanes with aromatic azomethine imines: access to fused 2,3-diazabicyclo[3.1.1]heptanes.
Yang, Xue-Chun; Wu, Feng; Wu, Wen-Biao; Zhang, Xu; Feng, Jian-Jun; Chemical science 15 (2024) 19488–19495; doi:10.1039/d4sc06334a

data_1573076
_publ_section_title
;
 Enantioselective dearomative formal (3+3) cycloadditions of
 bicyclobutanes with aromatic azomethine imines: access to fused
 2,3-diazabicyclo[3.1.1]heptanes.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              19488
_journal_page_last               19495
_journal_paper_doi               10.1039/d4sc06334a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C32 H24 Br F3 N4 O2'
_chemical_formula_sum            'C32 H24 Br F3 N4 O2'
_chemical_formula_weight         633.46
_chemical_name_systematic
(R)-(9-bromo-1-(1-methyl-1H-imidazole-2-carbonyl)-3-phenyl-1,2,3,11b-tetrahydro-4H-1,3-methanopyridazino[6,1-a]isoquinolin-4-yl)(4-(trifluoromethyl)phenyl)methanone
_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             2024-07-22
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-02 deposited with the CCDC.	2024-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.161(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.8729(2)
_cell_length_b                   12.87720(10)
_cell_length_c                   10.9786(2)
_cell_measurement_reflns_used    23677
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      73.6500
_cell_measurement_theta_min      3.3690
_cell_volume                     1423.59(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -27.00  20.00   1.00    1.00    --    0.00  57.00  90.00   47
  2  \w     39.00  85.00   1.00    1.00    --    0.00  57.00  90.00   46
  3  \w    -27.00   8.00   1.00    1.00    --    0.00  57.00  30.00   35
  4  \w     31.00  82.00   1.00    1.00    --    0.00  57.00  30.00   51
  5  \w    -66.00 -15.00   1.00    1.00    --    0.00 -57.00  60.00   51
  6  \w    -24.00  25.00   1.00    1.00    --    0.00  77.00  30.00   49
  7  \w    -25.00  75.00   1.00    1.00    --    0.00  57.00 -90.00  100
  8  \w     -1.00  37.00   1.00    1.00    --    0.00  37.00  90.00   38
  9  \w    -27.00  83.00   1.00    1.00    --    0.00  37.00-150.00  110
 10  \w     -9.00  24.00   1.00    1.00    --    0.00 -57.00  60.00   33
 11  \w     63.00  94.00   1.00    1.00    --   92.10  64.00 -48.36   31
 12  \w     45.00 108.00   1.00    1.00    --   92.10 -82.00 -60.00   63
 13  \w      4.00  29.00   1.00    1.00    --   92.10 -82.00 120.00   25
 14  \w     48.00 127.00   1.00    1.00    --   92.10 -82.00 120.00   79
 15  \w     59.00  85.00   1.00    1.00    --   92.10  79.00 136.91   26
 16  \w    134.00 162.00   1.00    1.00    --   92.10  63.00 133.20   28
 17  \w     66.00 118.00   1.00    1.00    --   92.10  50.00 -84.46   52
 18  \w    112.00 179.00   1.00    1.00    --   92.10  79.00 -11.05   67
 19  \w     57.00  90.00   1.00    1.00    --   92.10  82.00  30.00   33
 20  \w    141.00 167.00   1.00    1.00    --   92.10  77.00 -90.00   26
 21  \w     58.00  84.00   1.00    1.00    --   92.10  82.00-150.00   26
 22  \w    116.00 142.00   1.00    1.00    --   92.10  82.00-150.00   26
 23  \w     59.00  91.00   1.00    1.00    --   92.10  77.00  60.00   32
 24  \w     57.00  82.00   1.00    1.00    --   92.10  82.00-120.00   25
 25  \w     57.00 100.00   1.00    1.00    --   92.10  82.00   0.00   43
 26  \w    107.00 180.00   1.00    1.00    --   92.10  82.00   0.00   73
 27  \w     59.00  84.00   1.00    1.00    --   92.10  77.00 -60.00   25
 28  \w    103.00 129.00   1.00    1.00    --   92.10  77.00 -60.00   26
 29  \w      7.00  53.00   1.00    1.00    --   92.10 -61.00 -90.00   46
 30  \w     73.00 111.00   1.00    1.00    --   92.10 -61.00 -90.00   38
 31  \w     58.00  98.00   1.00    1.00    --   92.10  79.00 -11.05   40
 32  \w     64.00  92.00   1.00    1.00    --   92.10  63.00 133.20   28
 33  \w     59.00  98.00   1.00    1.00    --   92.10  77.00 -90.00   39
 34  \w      4.00 119.00   1.00    1.00    --   92.10 -82.00  30.00  115
 35  \w     65.00  90.00   1.00    1.00    --   92.10  62.00 109.17   25
 36  \w     59.00  84.00   1.00    1.00    --   92.10  77.00 -30.00   25
 37  \w     57.00  82.00   1.00    1.00    --   92.10  82.00 120.00   25
 38  \w     57.00  83.00   1.00    1.00    --   92.10  82.00 -90.00   26
 39  \w     62.00 126.00   1.00    1.00    --   92.10  30.00 -30.00   64
 40  \w     57.00  97.00   1.00    1.00    --   92.10  82.00 150.00   40
 41  \w     66.00 131.00   1.00    1.00    --   92.10  42.00-148.03   65
 42  \w     64.00 153.00   1.00    1.00    --   92.10  61.00 150.00   89
 43  \w     57.00  83.00   1.00    1.00    --   92.10  82.00  60.00   26
 44  \w     67.00  93.00   1.00    1.00    --   92.10  45.00  60.00   26
 45  \w    120.00 159.00   1.00    1.00    --   92.10  45.00  60.00   39
 46  \w     66.00  91.00   1.00    1.00    --   92.10  58.00-156.73   25
 47  \w     59.00  84.00   1.00    1.00    --   92.10  77.00  30.00   25
 48  \w      5.00 120.00   1.00    1.00    --   92.10 -61.00  30.00  115
 49  \w     57.00  82.00   1.00    1.00    --   92.10  82.00-180.00   25
 50  \w     59.00  84.00   1.00    1.00    --   92.10  77.00-150.00   25
 51  \w     57.00  83.00   1.00    1.00    --   92.10  82.00 -60.00   26
 52  \w     57.00  82.00   1.00    1.00    --   92.10  82.00  90.00   25
 53  \w    115.00 178.00   1.00    1.00    --   92.10  64.00 -48.36   63
 54  \w    125.00 181.00   1.00    1.00    --   92.10  50.00 -84.46   56
 55  \w     64.00 182.00   1.00    1.00    --   92.10  61.00-132.12  118
 56  \w     66.00 153.00   1.00    1.00    --   92.10  45.00  90.00   87
 57  \w    156.00 181.00   1.00    1.00    --   92.10  45.00  90.00   25
 58  \w     66.00 171.00   1.00    1.00    --   92.10  45.00 120.00  105
 59  \w      5.00  76.00   1.00    1.00    --   92.10 -82.00-180.00   71
 60  \w     93.00 128.00   1.00    1.00    --   92.10 -82.00-180.00   35
 61  \w     38.00 100.00   1.00    1.00    --   92.10 -82.00 -90.00   62
 62  \w     67.00 117.00   1.00    1.00    --   92.10  46.00   2.55   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0480203000
_diffrn_orient_matrix_UB_12      -0.0679709000
_diffrn_orient_matrix_UB_13      0.0887254000
_diffrn_orient_matrix_UB_21      -0.0097318000
_diffrn_orient_matrix_UB_22      0.0971266000
_diffrn_orient_matrix_UB_23      0.0778621000
_diffrn_orient_matrix_UB_31      -0.1450008000
_diffrn_orient_matrix_UB_32      0.0160372000
_diffrn_orient_matrix_UB_33      -0.0948784000
_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  0.0775
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            32191
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         4.348
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.457
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53908
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_description       block
_exptl_crystal_F_000             644
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2207 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.032(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     380
_refine_ls_number_reflns         5058
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0533P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0822
_refine_ls_wR_factor_ref         0.0842
_reflns_Friedel_coverage         0.904
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                4895
_reflns_number_total             5058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06334a2.cif
_cod_data_source_block           exp_4382_auto
_cod_depositor_comments
'Adding full bibliography for 1573075--1573076.cif.'
_cod_database_code               1573076
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.614
_shelx_estimated_absorpt_t_min   0.507
_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:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C10(H10), C11(H11), C13(H13), C15(H15), C16(H16), C20(H20),
 C21(H21), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30)
2.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C)
;
_shelx_res_checksum              66031
_shelx_hkl_checksum              46979
_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 4.223
_oxdiff_exptl_absorpt_empirical_full_min 0.423