Diastereoselective dearomative cycloaddition of bicyclobutanes with pyridinium ylides: a modular approach to multisubstituted azabicyclo[3.1.1]heptanes.
Dhake, Kushal; Woelk, Kyla J.; Krueckl, Liam D. N.; Alberts, Faith; Mutter, James; Pohl, Matthew O.; Thomas, Gilian T.; Sharma, Muskan; Bjornerud-Brown, Jaelyn; Fernández, Nahiane Pipaón; Schley, Nathan D.; Leitch, David C.; Chemical communications (Cambridge, England) 60 (2024) 13008–13011; doi:10.1039/d4cc04730c

data_7133838
_publ_section_title
;
 Diastereoselective dearomative cycloaddition of bicyclobutanes with
 pyridinium ylides: a modular approach to multisubstituted
 azabicyclo[3.1.1]heptanes.
;
_journal_issue                   89
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              13008
_journal_page_last               13011
_journal_paper_doi               10.1039/d4cc04730c
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C H2 Cl2, C24 H24 F N3 O3'
_chemical_formula_sum            'C25 H26 Cl2 F N3 O3'
_chemical_formula_weight         506.39
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2024-10-08 downloaded from the CCDC.
;
_cell_angle_alpha                109.987(4)
_cell_angle_beta                 96.545(3)
_cell_angle_gamma                110.033(3)
_cell_formula_units_Z            2
_cell_length_a                   9.8105(3)
_cell_length_b                   10.5343(4)
_cell_length_c                   13.5571(6)
_cell_measurement_reflns_used    9156
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.5620
_cell_measurement_theta_min      3.5740
_cell_volume                     1193.91(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.116a 64-bit (release 22-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.968
_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   -103.00 -19.00   1.00    1.00    --  -35.84 -57.00-150.00   84
  2  \w    -55.00  33.00   1.00    1.00    --  -35.84  38.00   0.00   88
  3  \w   -105.00 -17.00   1.00    1.00    --  -35.84 -38.00 120.00   88
  4  \w    -55.00  33.00   1.00    1.00    --  -35.84  38.00   0.00   88
  5  \w    -63.00  32.00   1.00    1.00    --  -35.84  77.00  90.00   95
  6  \w      8.00  42.00   1.00    1.00    --   35.84  79.00 140.70   34
  7  \w      9.00  42.00   1.00    1.00    --   35.84  77.00 -10.84   33
  8  \w      9.00  42.00   1.00    1.00    --   35.84  77.00-178.25   33
  9  \w     19.00 103.00   1.00    1.00    --   35.84  57.00  30.00   84
 10  \w    -31.00  53.00   1.00    1.00    --   35.84 -57.00 -90.00   84
 11  \w    -31.00  53.00   1.00    1.00    --   35.84 -57.00 -90.00   84
 12  \w      9.00  42.00   1.00    1.00    --   35.84  78.00 -55.99   33
 13  \w    -31.00  53.00   1.00    1.00    --   35.84 -57.00-120.00   84
 14  \w      9.00  42.00   1.00    1.00    --   35.84  78.00  43.89   33
 15  \w     19.00 103.00   1.00    1.00    --   35.84  57.00  30.00   84
 16  \w      9.00  42.00   1.00    1.00    --   35.84  78.00-131.57   33
 17  \w     41.00 135.00   1.00    8.00    --  108.40 -77.00 -30.00   94
 18  \w     40.00 126.00   1.00    8.00    --  108.40 -45.00 150.00   86
 19  \w     41.00 136.00   1.00    8.00    --  108.40 -79.00  64.60   95
 20  \w     38.00 130.00   1.00    8.00    --  108.40 -30.00 -30.00   92
 21  \w     87.00 178.00   1.00    8.00    --  108.40  30.00-120.00   91
 22  \w    103.00 176.00   1.00    8.00    --  108.40  77.00 150.00   73
 23  \w     91.00 177.00   1.00    8.00    --  108.40  45.00  60.00   86
 24  \w     38.00 130.00   1.00    8.00    --  108.40 -30.00-120.00   92
 25  \w     41.00 137.00   1.00    8.00    --  108.40 -80.00-149.71   96
 26  \w     41.00 136.00   1.00    8.00    --  108.40 -79.00   6.98   95
 27  \w     91.00 177.00   1.00    8.00    --  108.40  45.00 120.00   86
 28  \w     38.00 130.00   1.00    8.00    --  108.40 -30.00  60.00   92
 29  \w     41.00 136.00   1.00    8.00    --  108.40 -79.00  35.94   95
 30  \w     41.00 136.00   1.00    8.00    --  108.40 -79.00 -86.44   95
 31  \w     41.00 137.00   1.00    8.00    --  108.40 -80.00 147.40   96
 32  \w   -103.00 -19.00   1.00    1.00    --  -35.84 -57.00 -90.00   84
 33  \w    -63.00  32.00   1.00    1.00    --  -35.84  77.00   0.00   95
 34  \w   -103.00 -19.00   1.00    1.00    --  -35.84 -57.00 -60.00   84
 35  \w    -63.00  32.00   1.00    1.00    --  -35.84  77.00-120.00   95
 36  \w    -53.00  31.00   1.00    1.00    --  -35.84  57.00-180.00   84
 37  \w   -105.00 -17.00   1.00    1.00    --  -35.84 -38.00-150.00   88
 38  \w    -53.00  31.00   1.00    1.00    --  -35.84  57.00  30.00   84
 39  \w   -105.00 -17.00   1.00    1.00    --  -35.84 -38.00  30.00   88
 40  \w     19.00 103.00   1.00    1.00    --   35.84  57.00 120.00   84
 41  \w     10.00  36.00   1.00    1.00    --   35.84  75.00 -90.78   26
 42  \w    -21.00  63.00   1.00    1.00    --   35.84 -77.00 120.00   84
 43  \w      9.00  42.00   1.00    1.00    --   35.84  78.00  99.48   33
 44  \w     87.00 178.00   1.00    8.00    --  108.40  30.00   0.00   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1295121000
_diffrn_orient_matrix_UB_12      -0.0450851000
_diffrn_orient_matrix_UB_13      -0.0268719000
_diffrn_orient_matrix_UB_21      -0.0121197000
_diffrn_orient_matrix_UB_22      -0.0688876000
_diffrn_orient_matrix_UB_23      0.0839742000
_diffrn_orient_matrix_UB_31      -0.1143307000
_diffrn_orient_matrix_UB_32      -0.1493063000
_diffrn_orient_matrix_UB_33      -0.0890084000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            4533
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.732
_diffrn_reflns_theta_min         3.594
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.793
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.722
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       plate
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.582
_refine_diff_density_min         -0.573
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.202
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4533
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.202
_refine_ls_R_factor_all          0.0717
_refine_ls_R_factor_gt           0.0659
_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^)+5.1172P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1707
_refine_ls_wR_factor_ref         0.1731
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4016
_reflns_number_total             4533
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04730c2.cif
_cod_data_source_block           kjw-2024-220
_cod_depositor_comments
'Adding full bibliography for 7133838--7133839.cif.'
_cod_original_cell_volume        1193.91(9)
_cod_database_code               7133838
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23.5H26Cl2N4.5O4
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.679
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.738(4)
 0.262(4)
2. 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
3.a Ternary CH refined with riding coordinates:
 C2(H2), C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C4(H4A,H4B), C6(H6A,H6B)
3.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C16(H16), C17(H17),
 C20(H20)
3.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              88505
_shelx_hkl_checksum              80790
_olex2_date_sample_data_collection 2024-06-03
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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 1.320
_oxdiff_exptl_absorpt_empirical_full_min 0.864