Total synthesis of 1,4a-di-<i>epi-ent</i>-pancratistatin, exemplifying a stereodivergent approach to pancratistatin isomers.
Sun, Chunzhao; Inokuma, Tsubasa; Tsuji, Daisuke; Yamaoka, Yousuke; Akagi, Reiko; Yamada, Ken-Ichi; Chemical communications (Cambridge, England) 60 (2024) 6757–6760; doi:10.1039/d4cc02199a

data_7133155
_publ_section_title
;
 Total synthesis of 1,4a-di-<i>epi-ent</i>-pancratistatin, exemplifying a
 stereodivergent approach to pancratistatin isomers.
;
_journal_issue                   53
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6757
_journal_page_last               6760
_journal_paper_doi               10.1039/d4cc02199a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C H2 Cl2, C50 H37 N O13'
_chemical_formula_sum            'C51 H39 Cl2 N O13'
_chemical_formula_weight         944.73
_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             2022-04-06
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 79.3630(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.82580(10)
_cell_length_b                   13.1828(2)
_cell_length_c                   15.3126(2)
_cell_measurement_reflns_used    43309
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.7440
_cell_measurement_theta_min      2.9350
_cell_volume                     2147.78(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_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_temperature      93.00
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.965
_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    -84.00  94.00   0.50    0.64    --    5.00  31.00 174.32  356
  2  \w   -109.00  69.00   0.50    0.64    --  -20.00  40.00 171.25  356
  3  \w   -109.00  69.00   0.50    0.64    --  -20.00  40.00 171.25  356
  4  \w     35.00  61.00   0.50    0.64    --  -28.00  57.00  -7.96   52
  5  \w     35.00  61.00   0.50    0.64    --  -28.00  57.00 175.99   52
  6  \w     31.00  57.00   0.50    0.64    --  -32.00  54.00 134.65   52
  7  \w     28.00  57.00   0.50    0.64    --  -32.00  51.00  54.30   58
  8  \w     25.00  53.00   0.50    0.64    --  -36.00  49.00 174.12   56
  9  \w     26.00  53.00   0.50    0.64    --  -36.00  50.00  73.87   54
 10  \w      9.00  49.00   0.50    0.64    --  -40.00  45.00   4.07   80
 11  \w   -133.00  45.00   0.50    0.64    --  -44.00  43.00 174.95  356
 12  \w     19.00  45.00   0.50    0.64    --  -44.00  47.00 133.59   52
 13  \w   -136.00  43.00   0.50    0.64    --  -46.70   0.00   0.00  358
 14  \w   -136.00  43.00   0.50    0.64    --  -46.70  43.00 168.87  358
 15  \w      9.00  37.00   0.50    0.64    --  -52.00  45.00  -1.66   56
 16  \w   -145.00  33.00   0.50    0.64    --  -56.00  43.00 116.54  356
 17  \w   -145.00  33.00   0.50    0.64    --  -56.00  41.00  -8.05  356
 18  \w    -85.00  29.00   0.50    0.64    --  -60.00  39.00 178.76  228
 19  \w     -7.00  29.00   0.50    0.64    --  -60.00  42.00  82.20   72
 20  \w    -69.00 -43.00   0.50    0.64    --  -60.00  42.00  82.20   52
 21  \w     -1.00  25.00   0.50    0.64    --  -64.00  43.00 152.94   52
 22  \w    -61.00  25.00   0.50    0.64    --  -64.00  42.00   7.89  172
 23  \w   -152.00-127.00   0.50    0.64    --  -64.00  42.00   7.89   50
 24  \w     -1.00  25.00   0.50    0.64    --  -64.00  36.00 178.00   52
 25  \w    -14.00  21.00   0.50    0.64    --  -68.00  43.00  54.49   70
 26  \w    -11.00  21.00   0.50    0.64    --  -68.00  43.00  71.77   64
 27  \w    -11.00  15.00   0.50    0.64    --  -72.00  40.00 143.99   52
 28  \w     -9.00  17.00   0.50    0.64    --  -72.00  41.00 177.37   52
 29  \w     -8.00  17.00   0.50    0.64    --  -72.00  43.00  34.15   50
 30  \w   -158.00-133.00   0.50    0.64    --  -72.00  43.00  34.15   50
 31  \w    -27.00   8.00   0.50    2.57    --  -80.00  39.00 118.77   70
 32  \w    -27.00   5.00   0.50    2.57    --  -84.00  43.00  -7.58   64
 33  \w   -155.00-130.00   0.50    2.57    --  -84.00  43.00  -7.58   50
 34  \w    -24.00   4.00   0.50    2.57    --  -84.00  42.00  21.14   56
 35  \w   -155.00-129.00   0.50    2.57    --  -84.00  42.00  21.14   52
 36  \w    -21.00   5.00   0.50    2.57    --  -84.00  43.00 179.09   52
 37  \w    -27.00   5.00   0.50    2.57    --  -84.00  42.00 109.65   64
 38  \w    -92.00   1.00   0.50    2.57    --  -88.00  41.00  10.34  186
 39  \w   -167.00-119.00   0.50    2.57    --  -88.00  27.00 178.50   96
 40  \w    -84.00   1.00   0.50    2.57    --  -88.00  27.00 178.50  170
 41  \w    -47.00   1.00   0.50    2.57    --  -88.00  42.00  78.35   96
 42  \w    -25.00   1.00   0.50    2.57    --  -88.00  41.00 174.61   52
 43  \w   -129.00  -3.00   0.50    2.57    --  -92.00  43.00  41.21  252
 44  \w    -30.00  -4.00   0.50    2.57    --  -92.00  44.00 168.25   52
 45  \w    -98.00 -36.00   0.50    2.57    --  -97.40  55.00  -6.91  124
 46  \w   -187.00-159.00   0.50    2.57    --  -97.40  55.00  -6.91   56
 47  \w    -59.00  -8.00   0.50    2.57    --  -97.40   6.00 179.70  102
 48  \w    -61.00  -8.00   0.50    2.57    --  -97.40  40.00  60.00  106
 49  \w   -118.00 -67.00   0.50    2.57    --  -97.40  40.00  60.00  102
 50  \w   -144.00-119.00   0.50    2.57    --  -97.40   6.00 179.70   50
 51  \w   -187.00 -68.00   0.50    2.57    --  -97.40   0.00   0.00  238
 52  \w    -49.00 -15.00   0.50    2.57    --  -97.40  46.00 169.40   68
 53  \w   -145.00 -62.00   0.50    2.57    --  -97.40  46.00 169.40  166
 54  \w    -36.00  -8.00   0.50    2.57    --  -97.40  44.00  -8.29   56
 55  \w   -150.00 -14.00   0.50    2.57    --  -97.40  46.00 156.01  272
 56  \w    -58.00 -31.00   0.50    2.57    --  -97.40  53.00  -4.23   54
 57  \w    -89.00 -63.00   0.50    2.57    --  -97.40  60.00  96.37   52
 58  \w   -187.00-103.00   0.50    2.57    --  -97.40  44.00  -8.29  168
 59  \w   -187.00 -98.00   0.50    2.57    --  -97.40  60.00  96.37  178
 60  \w    -34.00  -8.00   0.50    2.57    --  -97.40  35.00  -8.97   52
 61  \w   -187.00-154.00   0.50    2.57    --  -97.40  35.00  -8.97   66
 62  \w   -187.00 -57.00   0.50    2.57    --  -97.40  60.00 178.15  260
 63  \w   -187.00 -79.00   0.50    2.57    --  -97.40  10.00   0.00  216
 64  \w   -187.00 -81.00   0.50    2.57    --  -97.40  60.00  -4.54  212
 65  \w   -109.00 -14.00   0.50    2.57    --  -97.40  46.00 108.49  190
 66  \w   -185.00-114.00   0.50    2.57    --  -97.40  46.00 108.49  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0881
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            55436
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.883
_diffrn_reflns_theta_min         2.936
_exptl_absorpt_coefficient_mu    1.976
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94011
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.461
_exptl_crystal_description       needle
_exptl_crystal_F_000             980
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.020
_refine_diff_density_min         -1.118
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details
;
 Flack x determined using 3218 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.086(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     605
_refine_ls_number_reflns         7908
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0849
_refine_ls_R_factor_gt           0.0816
_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^)+(0.1646P)^2^+2.1976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2214
_refine_ls_wR_factor_ref         0.2299
_reflns_Friedel_coverage         0.831
_reflns_Friedel_fraction_full    0.936
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                7597
_reflns_number_total             7908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02199a3.cif
_cod_data_source_block           220324yy2_auto
_cod_depositor_comments
'Adding full bibliography for 7133154--7133155.cif.'
_cod_database_code               7133155
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.693
_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:
 C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C011(H011)
2.b Secondary CH2 refined with riding coordinates:
 C01F(H01H,H01I), C01V(H01W,H01X)
2.c Aromatic/amide H refined with riding coordinates:
 C00W(H00W), C00X(H00X), C010(H010), C014(H014), C015(H015), C016(H016),
 C017(H017), C018(H018), C019(H019), C01A(H01A), C01B(H01B), C01D(H01F),
 C01E(H01G), C01G(H01J), C01H(H01K), C01I(H01L), C01K(H01M), C01L(H01N),
 C01M(H01O), C01O(H01P), C01P(H01Q), C01Q(H01R), C01R(H01S), C01S(H01T),
 C01T(H01U), C01U(H01V)
2.d Idealised Me refined as rotating group:
 C01C(H01C,H01D,H01E)
;
_shelx_res_checksum              82346
_shelx_hkl_checksum              36824
_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
;