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_7159217
_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         'C27 H44 O3 Si'
_chemical_formula_sum            'C27 H44 O3 Si'
_chemical_formula_weight         444.71
_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             2020-08-12
_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                92.2430(10)
_cell_angle_beta                 92.1110(10)
_cell_angle_gamma                102.967(2)
_cell_formula_units_Z            2
_cell_length_a                   6.38390(10)
_cell_length_b                   11.7026(2)
_cell_length_c                   17.9956(2)
_cell_measurement_reflns_used    22416
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6290
_cell_measurement_theta_min      2.4660
_cell_volume                     1307.69(4)
_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 0.963
_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    -76.00  -4.00   0.50    0.10    --  -46.75 108.00  42.00  144
  2  \w     24.00  79.00   0.50    0.10    --   46.75-108.00 -54.00  110
  3  \w   -139.00-104.00   0.50    0.40    --  -88.50-108.00 -54.00   70
  4  \w    -73.00 -48.00   0.50    0.40    --  -88.50 108.00  42.00   50
  5  \w     48.00 107.00   0.50    0.40    --  105.44-108.00 -54.00  118
  6  \w    113.00 154.00   0.50    0.40    --  105.44 108.00  42.00   82
  7  \w     -7.00  22.00   0.50    0.10    --   12.00  74.00 171.16   58
  8  \w    -26.00   0.00   0.50    0.10    --  -24.00 -76.00  80.75   52
  9  \w      7.00  32.00   0.50    0.10    --   28.00  70.00 -51.76   50
 10  \w      7.00  32.00   0.50    0.10    --   28.00  70.00-156.80   50
 11  \w     13.00  38.00   0.50    0.10    --   32.00  65.00  22.17   50
 12  \w     18.00  43.00   0.50    0.10    --   36.00  63.00 -37.32   50
 13  \w     18.00  43.00   0.50    0.10    --   36.00  63.00  91.90   50
 14  \w     18.00  43.00   0.50    0.10    --   36.00  63.00-115.06   50
 15  \w     22.00  48.00   0.50    0.10    --   36.00  60.00-157.84   52
 16  \w    -48.00 -23.00   0.50    0.10    --  -40.00 -61.00  17.83   50
 17  \w     31.00  57.00   0.50    0.10    --   40.00  57.00  51.21   52
 18  \w     23.00  48.00   0.50    0.10    --   40.00  59.00 163.19   50
 19  \w     23.00  48.00   0.50    0.10    --   40.00  60.00 -90.15   50
 20  \w    -60.00 -29.00   0.50    0.10    --  -46.75  57.00  60.00   62
 21  \w     -1.00  26.00   0.50    0.10    --  -46.75  57.00  60.00   54
 22  \w     59.00  95.00   0.50    0.10    --   46.75-125.00-150.00   72
 23  \w     34.00  59.00   0.50    0.10    --   46.75  52.00 141.41   50
 24  \w   -108.00 -82.00   0.50    0.10    --  -56.00 -56.00-117.42   52
 25  \w    -73.00 -40.00   0.50    0.10    --  -56.00 -56.00 -40.67   66
 26  \w    -70.00 -43.00   0.50    0.10    --  -56.00 -55.00-144.81   54
 27  \w   -128.00-102.00   0.50    0.10    --  -56.00 -56.00 137.15   52
 28  \w    -82.00 -41.00   0.50    0.10    --  -56.00 -56.00 137.15   82
 29  \w   -100.00 -75.00   0.50    0.10    --  -56.00 -56.00 -40.67   50
 30  \w   -127.00 -84.00   0.50    0.10    --  -56.00 -52.00  84.01   86
 31  \w    -76.00 -43.00   0.50    0.10    --  -56.00 -52.00  84.01   66
 32  \w    -68.00 -41.00   0.50    0.10    --  -56.00 -56.00-117.42   54
 33  \w   -113.00 -45.00   0.50    0.10    --  -60.00 -54.00  36.85  136
 34  \w   -117.00 -91.00   0.50    0.40    --  -68.00 -52.00 -14.60   52
 35  \w    -91.00 -52.00   0.50    0.40    --  -68.00 -55.00 -67.82   78
 36  \w    -91.00 -55.00   0.50    0.40    --  -68.00 -52.00 168.11   72
 37  \w    -78.00 -53.00   0.50    0.40    --  -68.00 -52.00 -14.60   50
 38  \w    -81.00 -55.00   0.50    0.40    --  -72.00 -54.00  79.70   52
 39  \w    -86.00 -60.00   0.50    0.40    --  -76.00 -51.00-120.13   52
 40  \w    -85.00 -60.00   0.50    0.40    --  -76.00 -56.00 -79.21   50
 41  \w    -87.00 -61.00   0.50    0.40    --  -76.00 -54.00-170.38   52
 42  \w    -85.00 -59.00   0.50    0.40    --  -76.00 -54.00  16.96   52
 43  \w    -91.00 -65.00   0.50    0.40    --  -80.00 -51.00  41.32   52
 44  \w    -91.00 -65.00   0.50    0.40    --  -80.00 -55.00 123.58   52
 45  \w    -89.00 -63.00   0.50    0.40    --  -80.00 -54.00 147.11   52
 46  \w    -90.00 -64.00   0.50    0.40    --  -80.00 -56.00 -22.86   52
 47  \w    -98.00 -73.00   0.50    0.40    --  -88.50 -54.00-170.25   50
 48  \w   -160.00-127.00   0.50    0.40    --  -88.50 -94.00-120.00   66
 49  \w   -121.00 -73.00   0.50    0.40    --  -88.50 -54.00  80.36   96
 50  \w   -108.00 -72.00   0.50    0.40    --  -88.50 -54.00 -89.29   72
 51  \w   -113.00 -74.00   0.50    0.40    --  -88.50 -55.00-174.24   78
 52  \w   -159.00-111.00   0.50    0.40    --  -88.50 -54.00 -89.29   96
 53  \w   -160.00-127.00   0.50    0.40    --  -88.50 -51.00 -51.35   66
 54  \w   -157.00-125.00   0.50    0.40    --  -88.50 -49.00-116.17   64
 55  \w    -98.00 -73.00   0.50    0.40    --  -88.50 -55.00 -32.76   50
 56  \w   -134.00-108.00   0.50    0.40    --  -88.50 -55.00 -32.76   52
 57  \w   -100.00 -74.00   0.50    0.40    --  -88.50 -55.00-136.05   52
 58  \w   -106.00 -72.00   0.50    0.40    --  -88.50 -51.00 -51.35   68
 59  \w   -100.00 -73.00   0.50    0.40    --  -88.50 -53.00 119.32   54
 60  \w   -106.00 -73.00   0.50    0.40    --  -88.50 -52.00-152.18   66
 61  \w   -159.00-113.00   0.50    0.40    --  -88.50 -52.00-152.18   92
 62  \w   -101.00 -75.00   0.50    0.40    --  -88.50 -49.00-116.17   52
 63  \w   -160.00-108.00   0.50    0.40    --  -88.50 -55.00-136.05  104
 64  \w   -155.00-129.00   0.50    0.40    --  -88.50 -54.00-170.25   52
 65  \w   -116.00 -74.00   0.50    0.40    --  -88.50 -53.00 -78.80   84
 66  \w   -144.00-118.00   0.50    0.40    --  -88.50 -77.00 -30.00   52
 67  \w   -159.00-123.00   0.50    0.40    --  -88.50 -55.00-174.24   72
 68  \w   -102.00 -76.00   0.50    0.40    --  -88.50 -52.00 152.11   52
 69  \w   -158.00-123.00   0.50    0.40    --  -88.50 -52.00 152.11   70
 70  \w   -100.00 -73.00   0.50    0.40    --  -88.50 -52.00  42.61   54
 71  \w    -48.00 -23.00   0.50    0.40    --  -88.50  45.00 120.00   50
 72  \w    -68.00 -19.00   0.50    0.40    --  -88.50  77.00-180.00   98
 73  \w   -106.00 -73.00   0.50    0.40    --  -88.50 -53.00  26.61   66
 74  \w   -157.00-122.00   0.50    0.40    --  -88.50 -53.00  26.61   70
 75  \w   -116.00 -73.00   0.50    0.40    --  -88.50 -52.00-129.01   86
 76  \w   -100.00 -74.00   0.50    0.40    --  -88.50 -53.00-118.71   52
 77  \w   -150.00-124.00   0.50    0.40    --  -88.50 -52.00-129.01   52
 78  \w   -102.00 -73.00   0.50    0.40    --  -88.50 -53.00 102.73   58
 79  \w   -109.00 -73.00   0.50    0.40    --  -88.50 -55.00  13.23   72
 80  \w    -99.00 -73.00   0.50    0.40    --  -88.50 -51.00 137.42   52
 81  \w   -145.00-119.00   0.50    0.40    --  -88.50 -55.00  13.23   52
 82  \w   -148.00-122.00   0.50    0.40    --  -88.50 -51.00 137.42   52
 83  \w   -158.00-133.00   0.50    0.40    --  -88.50 -53.00 170.63   50
 84  \w   -109.00 -74.00   0.50    0.40    --  -88.50 -53.00 170.63   70
 85  \w   -115.00 -81.00   0.50    0.40    --  -88.50 -56.00  -9.61   68
 86  \w   -160.00-124.00   0.50    0.40    --  -88.50 -56.00  -9.61   72
 87  \w     33.00 105.00   0.50    0.40    --  105.44 -94.00  90.00  144
 88  \w     33.00  96.00   0.50    0.40    --  105.44 -94.00-180.00  126
 89  \w     34.00  60.00   0.50    0.40    --  105.44 -61.00 120.00   52
 90  \w     35.00  71.00   0.50    0.40    --  105.44 -61.00-120.00   72
 91  \w     35.00 111.00   0.50    0.40    --  105.44-125.00 -90.00  152
 92  \w     34.00  60.00   0.50    0.40    --  105.44 -61.00  30.00   52
 93  \w     96.00 176.00   0.50    0.40    --  105.44  61.00  30.00  160
 94  \w    135.00 170.00   0.50    0.40    --  105.44  61.00 -30.00   70
 95  \w     92.00 131.00   0.50    0.40    --  105.44  61.00 -30.00   78
 96  \w     35.00 104.00   0.50    0.40    --  105.44 -94.00  60.00  138
 97  \w     56.00  99.00   0.50    0.40    --  105.44 -94.00 -30.00   86
 98  \w     77.00 105.00   0.50    0.40    --  105.44 -94.00   0.00   56
 99  \w     34.00  73.00   0.50    0.40    --  105.44 -94.00   0.00   78
100  \w     37.00  71.00   0.50    0.40    --  105.44 -61.00  90.00   68
101  \w     91.00 177.00   0.50    0.40    --  105.44  61.00  90.00  172
102  \w     33.00  58.00   0.50    0.40    --  105.44 -61.00 -60.00   50
103  \w    128.00 178.00   0.50    0.40    --  105.44  61.00  12.37  100
104  \w     93.00 123.00   0.50    0.40    --  105.44  61.00  12.37   60
105  \w     84.00 110.00   0.50    0.10    --   46.75  57.00  90.00   52
106  \w    -84.00 -36.00   0.50    0.10    --  -52.00 -56.00-153.16   96
107  \w   -128.00 -94.00   0.50    0.10    --  -56.00 -55.00  -4.07   68
108  \w    -68.00 -42.00   0.50    0.10    --  -56.00 -55.00  -4.07   52
109  \w    -66.00 -40.00   0.50    0.10    --  -56.00 -55.00  89.20   52
110  \w   -126.00-100.00   0.50    0.40    --  -76.00 -56.00 -48.39   52
111  \w    -87.00 -61.00   0.50    0.40    --  -76.00 -56.00  97.00   52
112  \w    -85.00 -60.00   0.50    0.40    --  -76.00 -56.00 -48.39   50
113  \w    -92.00 -67.00   0.50    0.40    --  -84.00 -54.00 -68.66   50
114  \w   -127.00 -77.00   0.50    0.40    --  -88.50 -52.00 157.71  100
115  \w   -109.00 -76.00   0.50    0.40    --  -88.50 -54.00  53.34   66
116  \w    -99.00 -73.00   0.50    0.40    --  -88.50 -53.00-162.96   52
117  \w   -157.00-131.00   0.50    0.40    --  -88.50 -53.00-162.96   52
118  \w   -158.00-132.00   0.50    0.40    --  -88.50 -54.00  53.34   52
119  \w    -71.00 -46.00   0.50    0.40    --  -88.50  61.00   0.00   50
120  \w     80.00 106.00   0.50    0.40    --  105.44 -99.00 103.86   52
121  \w     84.00 110.00   0.50    0.40    --  105.44-125.00 -60.00   52
122  \w     92.00 118.00   0.50    0.40    --  105.44  61.00 120.00   52
123  \w     80.00 105.00   0.50    0.40    --  105.44 -94.00  30.00   50
124  \w     33.00  59.00   0.50    0.40    --  105.44 -94.00  30.00   52
125  \w    100.00 143.00   0.50    0.40    --  105.44  62.00-133.10   86
126  \w     37.00  63.00   0.50    0.40    --  105.44 -61.00 120.00   52
127  \w    131.00 157.00   0.50    0.40    --  105.44  61.00 120.00   52
128  \w    122.00 162.00   0.50    0.40    --  105.44  15.00 -60.00   80
129  \w     37.00  66.00   0.50    0.40    --  105.44 -61.00-150.00   58
;
_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      0.0194343000
_diffrn_orient_matrix_UB_12      0.0404382000
_diffrn_orient_matrix_UB_13      0.0829693000
_diffrn_orient_matrix_UB_21      0.2359394000
_diffrn_orient_matrix_UB_22      0.0637919000
_diffrn_orient_matrix_UB_23      -0.0088063000
_diffrn_orient_matrix_UB_31      -0.0735680000
_diffrn_orient_matrix_UB_32      0.1121934000
_diffrn_orient_matrix_UB_33      -0.0198648000
_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  0.0590
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            39956
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.934
_diffrn_reflns_theta_min         2.460
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.969
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.398
_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    1.129
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.667
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 3815 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     575
_refine_ls_number_reflns         9535
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0200P)^2^+2.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1445
_refine_ls_wR_factor_ref         0.1457
_reflns_Friedel_coverage         0.819
_reflns_Friedel_fraction_full    0.882
_reflns_Friedel_fraction_max     0.789
_reflns_number_gt                9072
_reflns_number_total             9535
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00054k2.cif
_cod_data_source_block           hpd200
_cod_depositor_comments
'Adding full bibliography for 7159215--7159218.cif.'
_cod_database_code               7159217
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     SODXVI_060
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.796
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C5(H5), C1(H1), C13(H13), C39(H39), C40(H40), C28(H28), C32(H32), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C17(H17A,H17B), C29(H29A,H29B), C33(H33A,H33B),
 C38(H38A,H38B), C30(H30A,H30B), C14(H14A,H14B), C11(H11A,H11B), C44(H44A,H44B),
  C3(H3A,H3B), C37(H37A,H37B), C10(H10A,H10B), C41(H41A,H41B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C53(H53), C42(H42), C26(H26)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C51(H51A,H51B,H51C), C49(H49A,H49B,H49C), C21(H21A,H21B,
 H21C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C46(H46A,H46B,H46C), C19(H19A,
 H19B,H19C), C25(H25A,H25B,H25C), C23(H23A,H23B,H23C), C45(H45A,H45B,H45C),
 C18(H18A,H18B,H18C), C54(H54A,H54B,H54C), C48(H48A,H48B,H48C), C22(H22A,H22B,
 H22C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              58864
_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 1.824
_oxdiff_exptl_absorpt_empirical_full_min 0.652