Synthesis of menarandroside A from dehydroepiandrosterone.
Offei, Samuel D.; Arman, Hadi D.; Yoshimoto, Francis K.; Organic & biomolecular chemistry 21 (2023) 3172–3176; doi:10.1039/d3ob00054k

data_7159218
_publ_section_title
;
 Synthesis of menarandroside A from dehydroepiandrosterone.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3172
_journal_page_last               3176
_journal_paper_doi               10.1039/d3ob00054k
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H30 O3'
_chemical_formula_sum            'C20 H30 O3'
_chemical_formula_weight         318.44
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-11-20 deposited with the CCDC.	2023-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.52370(10)
_cell_length_b                   22.9939(2)
_cell_length_c                   9.71030(10)
_cell_measurement_reflns_used    45867
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6430
_cell_measurement_theta_min      3.8360
_cell_volume                     1679.87(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_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    -83.00  -9.00   0.50    0.11    --  -46.87 119.00 -22.00  148
  2  \w    -29.00  29.00   0.50    0.11    --  -46.87  15.00-108.00  116
  3  \w    101.00 178.00   0.50    0.42    --  106.69 115.00  70.00  154
  4  \w     50.00 133.00   0.50    0.42    --  106.69-156.00  96.00  166
  5  \w     89.00 178.00   0.50    0.42    --  106.69  15.00-108.00  178
  6  \w   -120.00 -83.00   0.50    0.11    --  -46.87 -57.00 -90.00   74
  7  \w   -120.00 -83.00   0.50    0.11    --  -46.87 -57.00 -60.00   74
  8  \w   -120.00 -83.00   0.50    0.11    --  -46.87 -57.00-180.00   74
  9  \w     83.00 120.00   0.50    0.11    --   46.87  57.00 -90.00   74
 10  \w    -51.00 -16.00   0.50    0.42    --  -88.50  45.00 150.00   70
 11  \w    -51.00 -16.00   0.50    0.42    --  -88.50  45.00-120.00   70
 12  \w     34.00  71.00   0.50    0.42    --  106.69 -61.00-120.00   74
 13  \w     34.00  71.00   0.50    0.42    --  106.69 -61.00 -60.00   74
 14  \w     34.00  71.00   0.50    0.42    --  106.69 -61.00-150.00   74
 15  \w   -120.00 -83.00   0.50    0.11    --  -46.87 -57.00-150.00   74
 16  \w   -121.00 -32.00   0.50    0.11    --  -46.87 -37.00 -30.00  178
 17  \w   -121.00 -52.00   0.50    0.11    --  -46.87 -37.00 150.00  138
 18  \w   -121.00 -32.00   0.50    0.11    --  -46.87 -37.00  60.00  178
 19  \w     64.00  91.00   0.50    0.42    --  106.69-165.00-165.00   54
 20  \w    -27.00  -2.00   0.50    0.11    --   12.00 107.00 143.51   50
 21  \w      2.00  27.00   0.50    0.11    --   24.00  74.00-136.62   50
 22  \w     18.00  43.00   0.50    0.11    --   36.00  63.00  54.76   50
 23  \w     18.00  43.00   0.50    0.11    --   36.00  63.00-179.03   50
 24  \w     18.00  43.00   0.50    0.11    --   36.00  62.00 126.10   50
 25  \w     18.00  44.00   0.50    0.11    --   36.00  62.00  97.18   52
 26  \w     21.00  47.00   0.50    0.11    --   36.00  61.00 -95.87   52
 27  \w    -52.00 -27.00   0.50    0.11    --  -40.00 -59.00  -9.18   50
 28  \w     24.00  49.00   0.50    0.11    --   40.00  58.00-147.71   50
 29  \w     23.00  48.00   0.50    0.11    --   40.00  60.00 -30.80   50
 30  \w     23.00  48.00   0.50    0.11    --   40.00  60.00  -2.60   50
 31  \w     36.00  78.00   0.50    0.11    --   46.87-125.00 -90.00   84
 32  \w    -67.00 -41.00   0.50    0.11    --  -56.00 -55.00 -65.67   52
 33  \w    -74.00 -40.00   0.50    0.11    --  -56.00 -55.00-172.33   68
 34  \w    -64.00 -39.00   0.50    0.11    --  -56.00 -54.00  18.54   50
 35  \w    -86.00 -43.00   0.50    0.11    --  -60.00 -54.00-124.18   86
 36  \w    -70.00 -44.00   0.50    0.11    --  -60.00 -54.00 -43.32   52
 37  \w    -74.00 -48.00   0.50    0.11    --  -64.00 -54.00 -80.49   52
 38  \w    -78.00 -52.00   0.50    0.42    --  -68.00 -55.00 129.49   52
 39  \w    -78.00 -52.00   0.50    0.42    --  -68.00 -51.00-148.26   52
 40  \w    -78.00 -52.00   0.50    0.42    --  -68.00 -55.00 151.95   52
 41  \w    -80.00 -54.00   0.50    0.42    --  -68.00 -51.00 -17.97   52
 42  \w    -77.00 -51.00   0.50    0.42    --  -68.00 -54.00 172.28   52
 43  \w    -83.00 -57.00   0.50    0.42    --  -72.00 -52.00  95.92   52
 44  \w    -84.00 -58.00   0.50    0.42    --  -72.00 -50.00  73.84   52
 45  \w   -133.00-107.00   0.50    0.42    --  -72.00 -50.00  73.84   52
 46  \w    -86.00 -60.00   0.50    0.42    --  -76.00 -56.00  68.15   52
 47  \w    -89.00 -64.00   0.50    0.42    --  -80.00 -56.00 -79.77   50
 48  \w    -90.00 -64.00   0.50    0.42    --  -80.00 -56.00  21.79   52
 49  \w    -90.00 -64.00   0.50    0.42    --  -80.00 -56.00 -98.34   52
 50  \w   -114.00 -74.00   0.50    0.42    --  -88.00 -55.00 157.18   80
 51  \w   -106.00 -72.00   0.50    0.42    --  -88.50 -54.00-137.58   68
 52  \w   -149.00-120.00   0.50    0.42    --  -88.50 -54.00  32.20   58
 53  \w   -158.00-118.00   0.50    0.42    --  -88.50 -52.00 -22.21   80
 54  \w   -115.00 -75.00   0.50    0.42    --  -88.50 -55.00 172.92   80
 55  \w   -112.00 -77.00   0.50    0.42    --  -88.50 -52.00 -11.85   70
 56  \w   -102.00 -72.00   0.50    0.42    --  -88.50 -54.00 104.60   60
 57  \w   -101.00 -73.00   0.50    0.42    --  -88.50 -52.00 -22.21   56
 58  \w   -102.00 -73.00   0.50    0.42    --  -88.50 -55.00-148.86   58
 59  \w   -100.00 -73.00   0.50    0.42    --  -88.50 -53.00  77.74   54
 60  \w   -152.00-126.00   0.50    0.42    --  -88.50 -55.00 172.92   52
 61  \w   -160.00-123.00   0.50    0.42    --  -88.50 -53.00  -2.27   74
 62  \w    -99.00 -73.00   0.50    0.42    --  -88.50 -52.00 -38.54   52
 63  \w   -126.00-100.00   0.50    0.42    --  -88.50 -52.00 -38.54   52
 64  \w   -100.00 -74.00   0.50    0.42    --  -88.50 -55.00  68.91   52
 65  \w   -121.00 -72.00   0.50    0.42    --  -88.50 -54.00 -55.38   98
 66  \w   -111.00 -72.00   0.50    0.42    --  -88.50 -54.00 -72.03   78
 67  \w   -105.00 -73.00   0.50    0.42    --  -88.50 -53.00   8.93   64
 68  \w   -158.00-124.00   0.50    0.42    --  -88.50 -53.00   8.93   68
 69  \w   -149.00-117.00   0.50    0.42    --  -88.50 -54.00 -72.03   64
 70  \w   -101.00 -75.00   0.50    0.42    --  -88.50 -52.00  49.53   52
 71  \w   -100.00 -74.00   0.50    0.42    --  -88.50 -55.00-100.76   52
 72  \w   -159.00-126.00   0.50    0.42    --  -88.50 -55.00-159.44   66
 73  \w   -116.00 -73.00   0.50    0.42    --  -88.50 -52.00-124.16   86
 74  \w   -157.00-120.00   0.50    0.42    --  -88.50 -55.00-148.86   74
 75  \w   -101.00 -73.00   0.50    0.42    --  -88.50 -55.00-110.91   56
 76  \w   -109.00 -75.00   0.50    0.42    --  -88.50 -54.00 142.94   68
 77  \w   -116.00 -78.00   0.50    0.42    --  -88.50 -54.00-173.82   76
 78  \w   -160.00-134.00   0.50    0.42    --  -88.50 -54.00-173.82   52
 79  \w    -97.00 -72.00   0.50    0.42    --  -88.50 -54.00  32.20   50
 80  \w    -45.00 -17.00   0.50    0.42    --  -88.50  45.00-150.00   56
 81  \w   -109.00 -74.00   0.50    0.42    --  -88.50 -48.00 115.97   70
 82  \w    -98.00 -73.00   0.50    0.42    --  -88.50 -55.00  61.17   50
 83  \w   -142.00-111.00   0.50    0.42    --  -88.50 -55.00  61.17   62
 84  \w   -104.00 -78.00   0.50    0.42    --  -88.50 -53.00  -2.27   52
 85  \w   -102.00 -76.00   0.50    0.42    --  -88.50 -55.00-159.44   52
 86  \w     79.00 111.00   0.50    0.42    --  106.69-125.00 -90.00   64
 87  \w     35.00  60.00   0.50    0.42    --  106.69-125.00 -90.00   50
 88  \w     66.00  92.00   0.50    0.42    --  106.69-125.00  90.00   52
 89  \w     35.00  61.00   0.50    0.42    --  106.69-125.00  90.00   52
 90  \w     34.00  66.00   0.50    0.42    --  106.69 -61.00  30.00   64
 91  \w     34.00  59.00   0.50    0.42    --  106.69 -61.00 -30.00   50
 92  \w     34.00  70.00   0.50    0.42    --  106.69 -61.00 150.00   72
 93  \w     38.00 107.00   0.50    0.42    --  106.69-102.00-101.15  138
 94  \w     34.00  69.00   0.50    0.42    --  106.69 -61.00  60.00   70
 95  \w     92.00 177.00   0.50    0.42    --  106.69  61.00  60.00  170
 96  \w     97.00 177.00   0.50    0.42    --  106.69  45.00  30.00  160
 97  \w    125.00 164.00   0.50    0.42    --  106.69  61.00 120.00   78
 98  \w     94.00 122.00   0.50    0.42    --  106.69  61.00 120.00   56
 99  \w     34.00 106.00   0.50    0.42    --  106.69-102.00 115.81  144
100  \w     36.00  93.00   0.50    0.42    --  106.69 -77.00 150.00  114
101  \w    108.00 134.00   0.50    0.42    --  106.69-165.00-165.00   52
102  \w    -27.00   1.00   0.50    0.11    --   12.00 107.00-172.19   56
103  \w     -5.00  21.00   0.50    0.11    --   20.00  81.00  89.27   52
104  \w     13.00  40.00   0.50    0.11    --   32.00  65.00-166.64   54
105  \w     13.00  39.00   0.50    0.11    --   32.00  66.00  97.13   52
106  \w     13.00  40.00   0.50    0.11    --   32.00  65.00  45.59   54
107  \w     13.00  40.00   0.50    0.11    --   32.00  65.00 131.80   54
108  \w     13.00  39.00   0.50    0.11    --   32.00  66.00   6.04   52
109  \w     14.00  42.00   0.50    0.11    --   32.00  64.00 -63.13   56
110  \w     18.00  44.00   0.50    0.11    --   36.00  63.00-119.87   52
111  \w     18.00  45.00   0.50    0.11    --   36.00  62.00 126.10   54
112  \w     18.00  44.00   0.50    0.11    --   36.00  63.00 -19.42   52
113  \w    -52.00 -23.00   0.50    0.11    --  -40.00 -59.00  -9.18   58
114  \w     23.00  52.00   0.50    0.11    --   40.00  59.00  88.44   58
115  \w     23.00  50.00   0.50    0.11    --   40.00  60.00 -30.80   54
116  \w   -120.00 -31.00   0.50    0.11    --  -46.87 -53.00  55.55  178
117  \w     34.00  96.00   0.50    0.11    --   46.87-125.00-120.00  124
118  \w     69.00 120.00   0.50    0.11    --   46.87 165.00-142.00  102
119  \w     34.00  96.00   0.50    0.11    --   46.87-125.00  90.00  124
120  \w   -128.00 -40.00   0.50    0.11    --  -56.00 -56.00 -29.97  176
121  \w   -128.00 -39.00   0.50    0.11    --  -56.00 -54.00  18.54  178
122  \w     40.00 129.00   0.50    0.11    --   56.00  55.00-179.45  178
123  \w   -132.00 -43.00   0.50    0.11    --  -60.00 -54.00 -14.44  178
124  \w   -132.00 -43.00   0.50    0.11    --  -60.00 -54.00 177.91  178
125  \w   -132.00 -44.00   0.50    0.11    --  -60.00 -55.00  50.66  176
126  \w   -132.00 -43.00   0.50    0.11    --  -60.00 -54.00-124.18  178
127  \w   -137.00 -49.00   0.50    0.11    --  -64.00 -52.00 -80.48  176
128  \w   -137.00 -49.00   0.50    0.11    --  -64.00 -49.00 116.50  176
129  \w     34.00 101.00   0.50    0.42    --  106.69 -77.00 120.00  134
130  \w     35.00  60.00   0.50    0.11    --   46.87-115.00 -18.00   50
131  \w    -26.00 100.00   0.50    0.11    --   46.87   0.00 -30.00  252
132  \w     32.00 122.00   0.50    0.11    --   46.87  19.00   0.00  180
133  \w    -26.00 120.00   0.50    0.11    --   46.87   0.00-180.00  292
134  \w    -26.00 120.00   0.50    0.11    --   46.87   0.00-150.00  292
135  \w    -26.00 120.00   0.50    0.11    --   46.87   0.00-120.00  292
136  \w    -26.00 120.00   0.50    0.11    --   46.87   0.00 -90.00  292
137  \w    -26.00 120.00   0.50    0.11    --   46.87   0.00 -60.00  292
138  \w   -128.00 -40.00   0.50    0.11    --  -56.00 -56.00 -96.32  176
139  \w   -137.00 -49.00   0.50    0.11    --  -64.00 -52.00 -15.24  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0847859000
_diffrn_orient_matrix_UB_12      0.0595678000
_diffrn_orient_matrix_UB_13      0.0315284000
_diffrn_orient_matrix_UB_21      -0.1846716000
_diffrn_orient_matrix_UB_22      0.0288055000
_diffrn_orient_matrix_UB_23      -0.0073967000
_diffrn_orient_matrix_UB_31      -0.0254547000
_diffrn_orient_matrix_UB_32      -0.0106311000
_diffrn_orient_matrix_UB_33      0.1552470000
_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  0.0623
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            70056
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.643
_diffrn_reflns_theta_min         1.921
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.650
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.527
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.259
_exptl_crystal_description       plate
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.184
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 2992 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         6803
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0656P)^2^+0.3040P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1143
_reflns_Friedel_coverage         0.905
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                6647
_reflns_number_total             6803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00054k2.cif
_cod_data_source_block           hpd137e
_cod_depositor_comments
'Adding full bibliography for 7159215--7159218.cif.'
_cod_database_code               7159218
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     'C3 OHC20 ALD LACTOL C!2 OH Mix 01_27_20'
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.890
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.709(2)
 0.291(2)
2. 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, All C(H,H,H,H) groups, All O(H) groups
3. Restrained distances
 O3-H3
 0.85 with sigma of 0.02
4.a Ternary CH refined with riding coordinates:
 C15(H15), C26(H26), C17(H17), C5(H5), C11(H11), C22(H22), C1(H1), C37(H37),
 C25(H25), C21(H21), C6(H6), C31(H31), C35(H35), C2(H2A)
4.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C36(H36A,H36B), C7(H7A,H7B), C13(H13A,H13B), C33(H33A,H33B),
 C24(H24A,H24B), C32(H32A,H32B), C23(H23A,H23B), C16(H16A,H16B), C27(H27A,H27B),
  C4(H4A,H4B), C10(H10A,H10B), C12(H12A,H12B), C3(H3A,H3B)
4.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C28(H28)
4.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C19(H19A,H19B,H19C), C40(H40A,H40B,H40C), C20(H20A,H20B,
 H20C)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O5(H5A), O6(H6A)
;
_shelx_res_checksum              46108
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.790
_oxdiff_exptl_absorpt_empirical_full_min 0.687