First total synthesis of asperilactone B. Revision of absolute stereochemistry of asperilactones B and C.
Djokić, Sanja; Benedeković, Goran; Kesić, Jelena; Rodić, Marko V; Popsavin, Mirjana; Popsavin, Velimir; Francuz, Jovana; Organic & biomolecular chemistry 22 (2024) 4864–4867; doi:10.1039/d4ob00583j

data_7159944
_publ_section_title
;
 First total synthesis of asperilactone B. Revision of absolute
 stereochemistry of asperilactones B and C.
;
_journal_issue                   24
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4864
_journal_page_last               4867
_journal_paper_doi               10.1039/d4ob00583j
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_enantioexcess_bulk     1
_chemical_enantioexcess_bulk_technique OA
_chemical_formula_moiety         'C8 H14 O6'
_chemical_formula_sum            'C8 H14 O6'
_chemical_formula_weight         206.19
_chemical_melting_point          365
_chemical_name_common            '(+)-Asperilactone B monohydrate'
_chemical_name_systematic
' 3,6-Anhydro--2,8-dideoxy-D-glycero-D-ido-octono-1,4-lactone monohydrate'
_chemical_optical_rotation       '[\a]^25^~D~ = +43.6 (c = 0.5, Me~2~CO)'
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_method           SHELXL-2019/3
_audit_update_record
;
2024-02-19 deposited with the CCDC.	2024-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.860(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4932(6)
_cell_length_b                   6.85772(19)
_cell_length_c                   8.9304(3)
_cell_measurement_reflns_used    3484
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      71.8450
_cell_measurement_theta_min      5.1290
_cell_volume                     976.30(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2020)'
_computing_publication_material  'ShelXle (H\"ubschle et al., 2011)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.3280
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -33.00  56.00   1.00    5.00    --   36.41 -37.00-150.00   89
  2  \w     17.00 106.00   1.00    5.00    --   36.41  37.00-180.00   89
  3  \w     61.00 109.00   1.00    5.00    --   36.41 178.00-180.00   48
  4  \w    -33.00  56.00   1.00    5.00    --   36.41 -37.00-150.00   89
  5  \w      1.00  74.00   1.00    5.00    --   36.41 -99.00-180.00   73
  6  \w     20.00 104.00   1.00    5.00    --   36.41  57.00-150.00   84
  7  \w     56.00 109.00   1.00    5.00    --   36.41-178.00 120.00   53
  8  \w     20.00 104.00   1.00    5.00    --   36.41  57.00 -60.00   84
  9  \w      1.00  74.00   1.00    5.00    --   36.41 -99.00 -30.00   73
 10  \w     20.00 104.00   1.00    5.00    --   36.41  54.00  -3.00   84
 11  \w     87.00 178.00   1.00   20.00    --  108.00  30.00-180.00   91
 12  \w     39.00  99.00   1.00   20.00    --  108.00 -94.00  30.00   60
 13  \w     41.00 109.00   1.00   20.00    --  108.00-111.00 -60.00   68
 14  \w     39.00  99.00   1.00   20.00    --  108.00 -94.00  30.00   60
 15  \w     70.00 121.00   1.00   20.00    --  108.00 -30.00-120.00   51
 16  \w    104.00 177.00   1.00   20.00    --  108.00   0.00 120.00   73
 17  \w     43.00  85.00   1.00   20.00    --  108.00   0.00 120.00   42
 18  \w     51.00 106.00   1.00   20.00    --  108.00 -94.00 -30.00   55
 19  \w     70.00  96.00   1.00   20.00    --  108.00 -94.00-150.00   26
 20  \w    102.00 152.00   1.00   20.00    --  108.00  77.00-150.00   50
 21  \w    105.00 131.00   1.00   20.00    --  108.00 -77.00  90.00   26
 22  \w     45.00 120.00   1.00   20.00    --  108.00 -45.00-120.00   75
 23  \w     44.00 106.00   1.00   20.00    --  108.00 -94.00 150.00   62
 24  \w     41.00 125.00   1.00   20.00    --  108.00 -45.00   0.00   84
 25  \w     48.00  90.00   1.00   20.00    --  108.00-111.00 150.00   42
 26  \w    109.00 175.00   1.00   20.00    --  108.00  77.00  30.00   66
 27  \w    -17.00   9.00   1.00    5.00    --   36.66 -77.00 -60.00   26
 28  \w     35.00  61.00   1.00    5.00    --   36.66 -99.00  60.00   26
 29  \w      1.00  26.00   1.00    5.00    --   36.66 -99.00  60.00   25
 30  \w    104.00 136.00   1.00   20.00    --  108.00 111.00 150.00   32
 31  \w    119.00 145.00   1.00   20.00    --  108.00 111.00 -60.00   26
 32  \w     67.00 105.00   1.00   20.00    --  108.00 -94.00  60.00   38
 33  \w     81.00 115.00   1.00   20.00    --  108.00 -15.00-180.00   34
 34  \w     20.00 104.00   1.00    5.00    --   36.66  57.00  60.00   84
 35  \w    -33.00  56.00   1.00    5.00    --   36.66 -37.00  60.00   89
 36  \w      0.00  26.00   1.00    5.00    --   36.66  94.00-142.98   26
 37  \w      4.00  35.00   1.00    5.00    --   36.66  87.00 153.67   31
 38  \w      2.00  28.00   1.00    5.00    --   36.66  92.00 -81.52   26
 39  \w      0.00  26.00   1.00    5.00    --   36.66  94.00  81.95   26
 40  \w    -33.00  56.00   1.00    5.00    --   36.66 -37.00 -30.00   89
 41  \w     20.00 104.00   1.00    5.00    --   36.66  57.00 120.00   84
 42  \w      5.00  37.00   1.00    5.00    --   36.66  85.00  18.88   32
 43  \w      7.00 108.00   1.00    5.00    --   36.66  19.00  30.00  101
 44  \w      2.00  28.00   1.00    5.00    --   36.66  92.00  71.18   26
 45  \w     20.00 104.00   1.00    5.00    --   36.66  57.00-120.00   84
 46  \w    -18.00  63.00   1.00    5.00    --   36.66 -77.00-150.00   81
 47  \w     90.00 155.00   1.00   20.00    --  108.00  61.00   0.00   65
 48  \w     70.00 178.00   1.00   20.00    --  108.00  15.00 -30.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Gemini S (Oxford Diffraction)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0140890000
_diffrn_orient_matrix_UB_12      -0.1841483000
_diffrn_orient_matrix_UB_13      -0.0888289000
_diffrn_orient_matrix_UB_21      -0.0606013000
_diffrn_orient_matrix_UB_22      -0.1145066000
_diffrn_orient_matrix_UB_23      0.0730246000
_diffrn_orient_matrix_UB_31      -0.0739561000
_diffrn_orient_matrix_UB_32      0.0587086000
_diffrn_orient_matrix_UB_33      -0.1364302000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            6007
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.059
_diffrn_reflns_theta_min         5.124
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.046
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72350
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022) 
Empirical absorption correction using spherical harmonics, 
implemented in SCALE3 ABSPACK scaling algorithm. 
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_description       plate
_exptl_crystal_F_000             440
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.698
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.057
_refine_diff_density_max         0.118
_refine_diff_density_min         -0.126
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
; 
 Flack x determined using 747 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.07(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     141
_refine_ls_number_reflns         1874
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0502P)^2^+0.1908P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.0923
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                1769
_reflns_number_total             1874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00583j3.cif
_cod_data_source_block           I
_cod_depositor_comments
'Adding full bibliography for 7159944--7159948.cif.'
_cod_original_sg_symbol_H-M      'C 2'
_cod_database_code               7159944
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_min   0.529
_shelx_estimated_absorpt_t_max   0.943
_shelx_res_checksum              53671