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_7133154
_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 ad
_chemical_formula_moiety         'C38 H39 N O8'
_chemical_formula_sum            'C38 H39 N O8'
_chemical_formula_weight         637.70
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-01-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.7775(2)
_cell_length_b                   19.6476(4)
_cell_length_c                   22.0751(5)
_cell_measurement_reflns_used    20341
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.9640
_cell_measurement_theta_min      2.0310
_cell_volume                     3373.28(13)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93.0
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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 -38.00   0.50    0.50    --    5.00  60.00  30.00   92
  2  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00 150.00  116
  3  \w   -136.00  43.00   0.50    0.50    --  -46.70  19.00 179.76  358
  4  \w   -136.00 -37.00   0.50    0.50    --  -46.70  60.00   0.00  198
  5  \w   -187.00 -35.00   0.50    0.50    --  -97.40  57.00  20.04  304
  6  \w   -187.00  -8.00   0.50    0.50    --  -97.40  41.00  -8.30  358
  7  \w   -109.00 -40.00   0.50    0.50    --  -97.40  59.00  -0.00  138
  8  \w   -130.00 -20.00   0.50    0.50    --  -97.40  47.00 160.65  220
  9  \w   -118.00 -92.00   0.50    0.50    --  -97.40  60.00 177.99   52
 10  \w    -82.00 -50.00   0.50    0.50    --  -97.40  60.00 177.99   64
 11  \w    -73.00 -19.00   0.50    0.50    --  -97.40  47.00  10.45  108
 12  \w   -187.00-150.00   0.50    0.50    --  -97.40  59.00  -0.00   74
 13  \w   -155.00  -9.00   0.50    0.50    --  -97.40  45.00  90.65  292
;
_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  0.0373
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            24441
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.267
_diffrn_reflns_theta_min         3.011
_exptl_absorpt_coefficient_mu    0.717
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73976
_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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       block
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.184
_refine_diff_density_min         -0.178
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 2394 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(9)
_refine_ls_extinction_coef       0.0025(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         6500
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0374
_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^)+(0.0489P)^2^+0.9781P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.751
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                6011
_reflns_number_total             6500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02199a3.cif
_cod_data_source_block           211228yyo_auto
_cod_depositor_comments
'Adding full bibliography for 7133154--7133155.cif.'
_cod_database_code               7133154
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C015 \\sim C019 \\sim C01B \\sim C016 \\sim C01A \\sim C017 \\sim C018: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C01C \\sim C3 \\sim C5 \\sim C0 \\sim C4 \\sim C1 \\sim C2: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
2. Rigid body (RIGU) restrains
 C015, C019, C01B, C016, C01A, C017, C018
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C01C, C3, C5, C0, C4, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C01C)=Sof(H01G)=Sof(H01H)=Sof(C3)=Sof(H3)=Sof(C2)=Sof(H2)=Sof(C1)=Sof(H1)=
 Sof(C0)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4)=1-FVAR(1)
 Sof(C015)=Sof(C017)=Sof(H017)=Sof(C019)=Sof(H019)=Sof(C016)=Sof(H016)=
 Sof(C01A)=Sof(H01D)=Sof(C018)=Sof(H018)=Sof(C01B)=Sof(H01E)=Sof(H01F)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C00A(H00A), C00C(H00C), C00E(H00E), C00M(H00M), C00N(H00N)
4.b Secondary CH2 refined with riding coordinates:
 C00G(H00B,H00D), C00I(H00F,H00G), C00O(H00I,H00J), C01B(H01E,H01F), C01C(H01G,
 H01H)
4.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011),
 C012(H012), C013(H013), C014(H014), C017(H017), C019(H019), C016(H016),
 C01A(H01D), C018(H018), C3(H3), C2(H2), C1(H1), C5(H5), C4(H4)
4.d Idealised Me refined as rotating group:
 C00T(H00K,H00L,H00O), C010(H01A,H01B,H01C)
;
_shelx_res_checksum              62281
_shelx_hkl_checksum              12670
_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
;