Copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations
Wang, Ze-Shu; Xu, Hao-Jin; Chen, Yang-Bo; Ye, Long-Wu; Zhou, Bo; Qian, Peng-Cheng; Chemical Communications  (2023) –; doi:10.1039/D3CC04817A

data_7132343
_publ_section_title
;
 Copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones
 with vinyl cations
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04817A
_journal_year                    2023
_chemical_formula_moiety         'C47 H40 Br N O7 S'
_chemical_formula_sum            'C47 H40 Br N O7 S'
_chemical_formula_weight         842.77
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2022-11-21
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-09-19 deposited with the CCDC.	2023-11-15 downloaded from the CCDC.
;
_cell_angle_alpha                97.822(2)
_cell_angle_beta                 104.257(2)
_cell_angle_gamma                117.863(2)
_cell_formula_units_Z            2
_cell_length_a                   13.2375(3)
_cell_length_b                   13.7370(3)
_cell_length_c                   14.5028(3)
_cell_measurement_reflns_used    28873
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.3490
_cell_measurement_theta_min      3.7830
_cell_volume                     2160.41(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -87.00  -6.00   1.00    1.00    --  -40.50 125.00   0.00   81
  2  \w    -53.00 -14.00   1.00    1.00    --  -40.50 125.00 -90.00   39
  3  \w    -78.00  -6.00   1.00    1.00    --  -40.50 125.00-180.00   72
  4  \w    -29.00  56.00   1.00    1.00    --   43.04 -37.00  90.00   85
  5  \w     22.00  76.00   1.00    1.00    --   43.04  37.00 -60.00   54
  6  \w     10.00  35.00   1.00    1.00    --   43.04  82.00-154.81   25
  7  \w     11.00  37.00   1.00    1.00    --   43.04  79.00  79.47   26
  8  \w     21.00 108.00   1.00    1.00    --   43.04  57.00  90.00   87
  9  \w     24.00 116.00   1.00    1.00    --   43.04  37.00-180.00   92
 10  \w     86.00 113.00   1.00    1.00    --   43.04  57.00 -30.00   27
 11  \w     12.00  41.00   1.00    1.00    --   43.04  78.00 -11.83   29
 12  \w     15.00  42.00   1.00    1.00    --   43.04  80.00 135.24   27
 13  \w     15.00  42.00   1.00    1.00    --   43.04  81.00  19.03   27
 14  \w     13.00  40.00   1.00    1.00    --   43.04  80.00 -91.36   27
 15  \w     17.00  88.00   1.00    1.00    --   43.04  57.00-120.00   71
 16  \w     18.00  67.00   1.00    1.00    --   43.04  57.00 -30.00   49
 17  \w     39.00 100.00   1.00    1.00    --   43.04  37.00  60.00   61
 18  \w    130.00 156.00   1.00    1.00    --  107.03  66.00  74.62   26
 19  \w     78.00 104.00   1.00    1.00    --  107.03  66.00  74.62   26
 20  \w     78.00 103.00   1.00    1.00    --  107.03  70.00   6.95   25
 21  \w     79.00 158.00   1.00    1.00    --  107.03  65.00  99.65   79
 22  \w     83.00 117.00   1.00    1.00    --  107.03  45.00 -30.00   34
 23  \w     79.00 105.00   1.00    1.00    --  107.03  61.00 -90.00   26
 24  \w     84.00 111.00   1.00    1.00    --  107.03  45.00 150.00   27
 25  \w     26.00 104.00   1.00    1.00    --  107.03 -94.00-180.00   78
 26  \w    114.00 178.00   1.00    1.00    --  107.03  67.00-131.04   64
 27  \w     36.00  94.00   1.00    1.00    --  107.03-125.00  60.00   58
 28  \w    124.00 150.00   1.00    1.00    --  107.03  64.00 149.08   26
 29  \w     79.00 176.00   1.00    1.00    --  107.03  61.00 120.00   97
 30  \w     84.00 109.00   1.00    1.00    --  107.03  45.00   0.00   25
 31  \w     83.00 110.00   1.00    1.00    --  107.03  45.00-120.00   27
 32  \w     49.00 112.00   1.00    1.00    --  107.03-125.00 120.00   63
 33  \w     78.00 104.00   1.00    1.00    --  107.03  67.00-131.04   26
 34  \w     45.00 126.00   1.00    1.00    --  107.03 -61.00-150.00   81
 35  \w     79.00 176.00   1.00    1.00    --  107.03  62.00-176.63   97
 36  \w     79.00 104.00   1.00    1.00    --  107.03  62.00 167.70   25
 37  \w     80.00 105.00   1.00    1.00    --  107.03  64.00 149.08   25
 38  \w     79.00 106.00   1.00    1.00    --  107.03  61.00  30.00   27
 39  \w    111.00 150.00   1.00    1.00    --  107.03  61.00  30.00   39
 40  \w     79.00 105.00   1.00    1.00    --  107.03  61.00   0.00   26
 41  \w     66.00 107.00   1.00    1.00    --  107.03 -94.00 -30.00   41
 42  \w     80.00 177.00   1.00    1.00    --  107.03  61.00 -30.00   97
 43  \w     83.00 109.00   1.00    1.00    --  107.03  45.00 -90.00   26
 44  \w     80.00 105.00   1.00    1.00    --  107.03  61.00  90.00   25
 45  \w     79.00 105.00   1.00    1.00    --  107.03  61.00  60.00   26
 46  \w     81.00 106.00   1.00    1.00    --  107.03  59.00  11.47   25
 47  \w     79.00 105.00   1.00    1.00    --  107.03  61.00-150.00   26
 48  \w     85.00 165.00   1.00    1.00    --  107.03  45.00 -60.00   80
 49  \w     79.00 106.00   1.00    1.00    --  107.03  62.00 -64.48   27
 50  \w     84.00 177.00   1.00    1.00    --  107.03  45.00  60.00   93
 51  \w     81.00 108.00   1.00    1.00    --  107.03  52.00 -31.21   27
 52  \w     76.00 103.00   1.00    1.00    --  107.03 -94.00-120.00   27
 53  \w     82.00 108.00   1.00    1.00    --  107.03  50.00-146.14   26
 54  \w     27.00  56.00   1.00    1.00    --  107.03 -94.00-120.00   29
 55  \w     38.00 110.00   1.00    1.00    --  107.03-125.00-180.00   72
 56  \w     82.00 108.00   1.00    1.00    --  107.03  54.00 152.18   26
 57  \w    115.00 147.00   1.00    1.00    --  107.03  70.00   6.95   32
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0819765000
_diffrn_orient_matrix_UB_12      0.0241173000
_diffrn_orient_matrix_UB_13      0.0463279000
_diffrn_orient_matrix_UB_21      0.0509993000
_diffrn_orient_matrix_UB_22      -0.0266830000
_diffrn_orient_matrix_UB_23      0.0942959000
_diffrn_orient_matrix_UB_31      0.1024081000
_diffrn_orient_matrix_UB_32      0.1277138000
_diffrn_orient_matrix_UB_33      0.0458655000
_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  0.0208
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            35996
_diffrn_reflns_point_group_measured_fraction_full 0.906
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.315
_diffrn_reflns_theta_min         3.289
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.159
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80298
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             872
_refine_diff_density_max         1.464
_refine_diff_density_min         -1.352
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 6286 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1037
_refine_ls_number_reflns         15457
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0375
_refine_ls_shift/su_max          0.020
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0482P)^2^+2.2587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.0973
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    0.813
_reflns_Friedel_fraction_max     0.768
_reflns_number_gt                15043
_reflns_number_total             15457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04817a2.cif
_cod_data_source_block           exp_17663_auto
_cod_depositor_comments
;

2024-06-28
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C94 H80 Br2 N2 O14 S2'
_cod_original_formula_weight         1685.54
_cod_original_formula_moiety         '2(C47 H40 Br N O7 S)'
_cod_original_formula_units_Z            1
_cod_original_cell_volume        2160.40(9)
_cod_database_code               7132343
_shelx_shelxl_version_number     2018/3
_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
2. Restrained distances
 Br01_$1-O00Z_$2
 3.1 with sigma of 0.001
3.a Ternary CH refined with riding coordinates:
 C024(H024), C02V(H02V)
3.b Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00K(H00K), C00N(H00N), C00Q(H00Q), C00R(H00R), C00T(H00T),
 C00U(H00U), C010(H010), C011(H011), C015(H015), C018(H018), C019(H019),
 C01A(H01A), C01B(H01B), C01D(H01D), C01F(H01F), C01I(H01I), C01J(H01J),
 C01K(H01K), C01L(H01L), C01M(H01M), C01P(H01P), C01Q(H01Q), C01S(H01S),
 C01U(H01U), C01V(H01V), C020(H020), C021(H021), C025(H025), C027(H027),
 C028(H028), C02B(H02B), C02C(H02C), C02H(H02Q), C02I(H02R), C02K(H02S),
 C02M(H02), C02N(H02N), C02O(H02O), C02S(H1), C02U(H3), C02W(H02W), C02X(H02X),
 C02Y(H02Y), C02Z(H4), C032(H032), C033(H033), C035(H035)
3.c Idealised Me refined as rotating group:
 C029(H02L,H02M,H02P), C02G(H02A,H02D,H02E), C02J(H02F,H02G,H02H), C02L(H02T,
 H02U,H02Z), C02P(H02I,H02J,H02K), C02T(H2,H,HA), C031(H03G,H03H,H03I),
 C034(H03J,H03K,H03L), C037(H03A,H03B,H03C), C039(H03D,H03E,H03F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              36779
_shelx_hkl_checksum              64841
_shelx_fab_checksum              59910
_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 1.284
_oxdiff_exptl_absorpt_empirical_full_min 0.874