Divergent oxidative dearomatization coupling reactions to construct polycyclic cyclohexadienones
Pu, Qian; Huo, Mingming; Liang, Guojuan; Bai, Lijuan; Chen, Genhui; Li, Hongjiao; Xiang, Peng; Zhou, Hui; Zhou, Jing; Chemical Communications  (2022) –; doi:10.1039/D2CC00183G

data_7129853
_publ_section_title
;
 Divergent oxidative dearomatization coupling reactions to construct
 polycyclic cyclohexadienones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00183G
_journal_year                    2022
_chemical_formula_moiety         '2(C31 H31 Br O2), C H4 O'
_chemical_formula_sum            'C63 H66 Br2 O5'
_chemical_formula_weight         1062.97
_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     direct
_audit_creation_date             2021-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-08 deposited with the CCDC.	2022-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                107.066(2)
_cell_angle_beta                 90.028(2)
_cell_angle_gamma                112.861(3)
_cell_formula_units_Z            2
_cell_length_a                   11.4412(3)
_cell_length_b                   13.3055(4)
_cell_length_c                   21.0185(6)
_cell_measurement_reflns_used    5550
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7580
_cell_measurement_theta_min      3.7890
_cell_volume                     2794.60(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  11.00   0.50    5.00    --  -33.50   0.00-180.00  232
  2  \w    -66.00 -13.00   0.50    5.00    --  -33.50 -37.00 -60.00  106
  3  \w    -80.00 -36.00   0.50    5.00    --  -33.50 178.00-150.00   88
  4  \w     58.00 110.00   0.50    5.00    --   36.47 178.00 120.00  104
  5  \w     27.00  61.00   0.50    5.00    --   36.47  57.00-180.00   68
  6  \w     40.00  76.00   0.50    5.00    --   36.47 -99.00  60.00   72
  7  \w     67.00  98.00   0.50    5.00    --   36.47  37.00 -90.00   62
  8  \w     58.00  98.00   0.50    5.00    --   36.47 178.00 150.00   80
  9  \w     79.00 104.00   0.50    5.00    --   36.47  57.00 150.00   50
 10  \w     70.00  96.00   0.50    5.00    --   36.47-133.00 -71.00   52
 11  \w     30.00  56.00   0.50    5.00    --   36.47-133.00 -71.00   52
 12  \w     64.00  91.00   0.50    5.00    --   36.47  57.00-180.00   54
 13  \w     25.00  63.00   0.50    5.00    --   36.47  57.00 150.00   76
 14  \w     14.00  97.00   0.50    5.00    --   36.47  37.00 150.00  166
 15  \w     58.00  85.00   0.50    5.00    --   36.47 178.00  60.00   54
 16  \w     73.00 107.00   0.50    5.00    --   36.47 178.00 -60.00   68
 17  \w     61.00 108.00   0.50    5.00    --   36.47 178.00  30.00   94
 18  \w     15.00  57.00   0.50    5.00    --   36.47  37.00 -90.00   84
 19  \w    115.00 142.00   0.50   21.00    --  108.00 178.00  60.00   54
 20  \w     39.00 112.00   0.50   21.00    --  108.00 -45.00 -90.00  146
 21  \w     69.00 112.00   0.50   21.00    --  108.00-111.00-180.00   86
 22  \w     56.00 108.00   0.50   21.00    --  108.00 -94.00  90.00  104
 23  \w     82.00 112.00   0.50   21.00    --  108.00-111.00 -90.00   60
 24  \w     41.00 109.00   0.50   21.00    --  108.00 -94.00   0.00  136
 25  \w     38.00  63.00   0.50   21.00    --  108.00-111.00 -90.00   50
 26  \w     41.00 126.00   0.50   21.00    --  108.00 -45.00 150.00  170
 27  \w     93.00 157.00   0.50   21.00    --  108.00  45.00 -60.00  128
 28  \w    100.00 132.00   0.50   21.00    --  108.00 111.00-120.00   64
 29  \w     38.00 125.00   0.50   21.00    --  108.00 -45.00  60.00  174
 30  \w     83.00 119.00   0.50   21.00    --  108.00 -45.00 -60.00   72
 31  \w    106.00 167.00   0.50   21.00    --  108.00 111.00-150.00  122
 32  \w     40.00  70.00   0.50   21.00    --  108.00 -45.00 -60.00   60
 33  \w     56.00 136.00   0.50   21.00    --  108.00 -77.00-180.00  160
 34  \w     38.00 177.00   0.50   21.00    --  108.00   0.00-120.00  278
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0826007000
_diffrn_orient_matrix_UB_12      -0.0097359000
_diffrn_orient_matrix_UB_13      -0.0612549000
_diffrn_orient_matrix_UB_21      -0.0777852000
_diffrn_orient_matrix_UB_22      0.0540996000
_diffrn_orient_matrix_UB_23      0.0471848000
_diffrn_orient_matrix_UB_31      0.0940598000
_diffrn_orient_matrix_UB_32      0.1206329000
_diffrn_orient_matrix_UB_33      0.0009771000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            20408
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.743
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.206
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.915
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     656
_refine_ls_number_reflns         9972
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0889
_refine_ls_R_factor_gt           0.0667
_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^)+(0.1153P)^2^+1.0451P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1862
_refine_ls_wR_factor_ref         0.2105
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7068
_reflns_number_total             9972
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00183g2.cif
_cod_data_source_block           202111241
_cod_original_cell_volume        2794.59(14)
_cod_database_code               7129853
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N2Br1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.762
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O3-C32
 1.45 with sigma of 0.02
 O3A-C32A
 1.45 with sigma of 0.02
3. Rigid bond restraints
 Br1', C1'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C1') \\sim Ueq, Uanis(Br1') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C32A) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3) = Uanis(O3A)
Uanis(C32) = Uanis(C32A)
5. Others
 Sof(O3A)=Sof(H3AA)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(O3)=Sof(H3A)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C23(H23), C2'(H2'), C3'(H3'), C4'(H4'), C5'(H5'),
  C10'(H10'), C11'(H11'), C14'(H14'), C15'(H15'), C16'(H16'), C17'(H17'),
 C19'(H19'), C23'(H23')
6.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C25'(H25D,H25E,H25F),
 C26'(H26D,H26E,H26F), C27'(H27D,H27E,H27F), C29'(H29D,H29E,H29F), C30'(H30D,
 H30E,H30F), C31'(H31D,H31E,H31F), C32(H32A,H32B,H32C), C32A(H32D,H32E,H32F)
6.c Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1'(H1'), O3(H3A), O3A(H3AA)
;
_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 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.916