Enolate addition to bicyclobutanes enables expedient access to 2-oxo-bicyclohexane scaffolds
Woelk, Kyla; Dhake, Kushal; Schley, Nathan D.; Leitch, David; Chemical Communications  (2023) –; doi:10.1039/D3CC04234K

data_7132198
_publ_section_title
;
 Enolate addition to bicyclobutanes enables expedient access to
 2-oxo-bicyclohexane scaffolds
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04234K
_journal_year                    2023
_chemical_formula_moiety         'C19 H22 N2 O4'
_chemical_formula_sum            'C19 H22 N2 O4'
_chemical_formula_weight         342.38
_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   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2gw3hz
_audit_creation_date             2023-02-19
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-08-22 deposited with the CCDC.	2023-10-10 downloaded from the CCDC.
;
_cell_angle_alpha                85.949(6)
_cell_angle_beta                 78.293(6)
_cell_angle_gamma                80.362(6)
_cell_formula_units_Z            2
_cell_length_a                   6.8191(4)
_cell_length_b                   10.9500(8)
_cell_length_c                   12.1182(10)
_cell_measurement_reflns_used    3745
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.4710
_cell_measurement_theta_min      3.7000
_cell_volume                     872.90(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.71a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.71a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.71a (Rigaku OD, 2022)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.974
_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   -105.00 -17.00   1.00    3.00    --  -36.07 -38.00 120.00   88
  2  \w    -63.00  31.00   1.00    3.00    --  -36.07  77.00  60.00   94
  3  \w    -53.00  31.00   1.00    3.00    --  -36.07  57.00  60.00   84
  4  \w    -55.00  33.00   1.00    3.00    --  -36.07  38.00   0.00   88
  5  \w   -103.00 -19.00   1.00    3.00    --  -36.07 -57.00-150.00   84
  6  \w    -63.00  31.00   1.00    3.00    --  -36.07  77.00 -60.00   94
  7  \w    -21.00  63.00   1.00    3.00    --   36.07 -77.00-150.00   84
  8  \w    -21.00  63.00   1.00    3.00    --   36.07 -77.00 120.00   84
  9  \w      5.00  33.00   1.00    3.00    --   36.07  84.00  -1.78   28
 10  \w      4.00  31.00   1.00    3.00    --   36.07  86.00 118.78   27
 11  \w    -33.00  55.00   1.00    3.00    --   36.07 -38.00  60.00   88
 12  \w     40.00 106.00   1.00   18.00    --  108.40 -89.00  26.17   66
 13  \w    103.00 176.00   1.00   18.00    --  108.40  77.00  90.00   73
 14  \w     41.00 135.00   1.00   18.00    --  108.40 -77.00  90.00   94
 15  \w     42.00 126.00   1.00   18.00    --  108.40 -61.00-180.00   84
 16  \w     39.00 106.00   1.00   18.00    --  108.40 -90.00 -15.95   67
 17  \w     38.00 130.00   1.00   18.00    --  108.40 -30.00 120.00   92
 18  \w     38.00 130.00   1.00   18.00    --  108.40 -30.00-180.00   92
 19  \w    103.00 176.00   1.00   18.00    --  108.40  77.00 150.00   73
 20  \w    103.00 176.00   1.00   18.00    --  108.40  77.00 120.00   73
 21  \w     91.00 177.00   1.00   18.00    --  108.40  45.00-180.00   86
 22  \w     40.00 126.00   1.00   18.00    --  108.40 -45.00  30.00   86
 23  \w     41.00 135.00   1.00   18.00    --  108.40 -77.00 -60.00   94
 24  \w     40.00 106.00   1.00   18.00    --  108.40 -89.00 -67.55   66
 25  \w     39.00 106.00   1.00   18.00    --  108.40 -90.00-131.83   67
 26  \w     87.00 178.00   1.00   18.00    --  108.40  30.00  90.00   91
 27  \w     39.00 106.00   1.00   18.00    --  108.40 -90.00 140.61   67
 28  \w   -103.00 -19.00   1.00    3.00    --  -36.07 -57.00   0.00   84
 29  \w   -105.00 -17.00   1.00    3.00    --  -36.07 -38.00  60.00   88
 30  \w   -103.00 -19.00   1.00    3.00    --  -36.07 -57.00 -60.00   84
 31  \w    -65.00  35.00   1.00    3.00    --  -36.07  19.00 -90.00  100
 32  \w      2.00  29.00   1.00    3.00    --   36.07  90.00  61.51   27
 33  \w      3.00  30.00   1.00    3.00    --   36.07  89.00 154.86   27
;
_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      -0.0073851000
_diffrn_orient_matrix_UB_12      0.1067095000
_diffrn_orient_matrix_UB_13      0.0777963000
_diffrn_orient_matrix_UB_21      0.0077457000
_diffrn_orient_matrix_UB_22      -0.0935601000
_diffrn_orient_matrix_UB_23      0.1007152000
_diffrn_orient_matrix_UB_31      0.2333587000
_diffrn_orient_matrix_UB_32      -0.0159232000
_diffrn_orient_matrix_UB_33      -0.0261516000
_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  0.0530
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9350
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.782
_diffrn_reflns_theta_min         3.728
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.753
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.882
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.71a (Rigaku Oxford Diffraction, 2022)
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    1.303
_exptl_crystal_description       block
_exptl_crystal_F_000             364
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.553
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         3346
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0722
_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^)+(0.1357P)^2^+0.3239P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1978
_refine_ls_wR_factor_ref         0.2161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2644
_reflns_number_total             3346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04234k2.cif
_cod_data_source_block           kwj-2023-413a
_cod_database_code               7132198
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H24N2O3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.889
_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. Restrained distances
 N2-C8 \\sim N2A-C8
 with sigma of 0.02
 C12-C11 \\sim C9A-C10A \\sim C9-C10 \\sim C12A-C11A
 with sigma of 0.02
 O4-C10 \\sim C11A-O4A \\sim C11-O4 \\sim O4A-C10A
 with sigma of 0.02
 N2A-C8 \\sim N2-C8
 with sigma of 0.02
 N2A-C12A \\sim N2-C9 \\sim N2-C12 \\sim N2A-C9A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O4A, N2A, C9A, C10A, C11A, C12A, O4, N2, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(O4A)=Sof(N2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10C)=Sof(H10D)=
 Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(C12A)=Sof(H12C)=Sof(H12D)=1-FVAR(1)
 Sof(O4)=Sof(N2)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(C11)=Sof(H12A)=Sof(H12B)=Sof(C12)=Sof(H13A)=Sof(H13B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C9A(H9AA,H9AB), C10A(H10C,H10D), C11A(H11A,H11B),
 C12A(H12C,H12D), C9(H9A,H9B), C10(H10A,H10B), C11(H12A,H12B), C12(H13A,H13B)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C17(H17), C18(H18)
5.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              45785
_shelx_hkl_checksum              77370
_olex2_date_sample_data_collection 2023-02-15
_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 1.379
_oxdiff_exptl_absorpt_empirical_full_min 0.636