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_7159215
_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 O5 Si, C27 H44.25 O4.25 Si'
_chemical_formula_sum            'C54 H88.25 O9.25 Si2'
_chemical_formula_weight         941.67
_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_block_doi                 10.5517/ccdc.csd.cc26nh3h
_audit_creation_date             2020-11-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-11-20 deposited with the CCDC.	2023-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                93.4492(4)
_cell_angle_beta                 95.0225(4)
_cell_angle_gamma                103.0518(5)
_cell_formula_units_Z            1
_cell_length_a                   6.36191(4)
_cell_length_b                   11.81085(7)
_cell_length_c                   18.04153(8)
_cell_measurement_reflns_used    38681
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.0330
_cell_measurement_theta_min      2.4720
_cell_volume                     1311.071(13)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_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 0.969
_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    -93.00 -18.00   0.50    0.08    --  -46.87 135.00-169.00  150
  2  \w   -120.00 -68.00   0.50    0.08    --  -46.87-133.00 -56.00  104
  3  \w   -120.00 -67.00   0.50    0.08    --  -46.87-135.00 124.00  106
  4  \w    -92.00 -17.00   0.50    0.08    --  -46.87 133.00  11.00  150
  5  \w     39.00 100.00   0.50    0.08    --   46.87-133.00 -56.00  122
  6  \w     40.00 101.00   0.50    0.08    --   46.87-135.00 124.00  122
  7  \w    -91.00 -17.00   0.50    0.31    --  -88.50 133.00  11.00  148
  8  \w    -94.00 -18.00   0.50    0.31    --  -88.50 135.00-169.00  152
  9  \w   -160.00 -67.00   0.50    0.31    --  -88.50-135.00 124.00  186
 10  \w   -160.00 -68.00   0.50    0.31    --  -88.50-133.00 -56.00  184
 11  \w     90.00 178.00   0.50    0.31    --  106.69 133.00  11.00  176
 12  \w     89.00 178.00   0.50    0.31    --  106.69 135.00-169.00  178
 13  \w     39.00 118.00   0.50    0.31    --  106.69-133.00 -56.00  158
 14  \w     40.00 119.00   0.50    0.31    --  106.69-135.00 124.00  158
 15  \w    -16.00  10.00   0.50    0.08    --   16.00  95.00 -19.55   52
 16  \w      1.00  27.00   0.50    0.08    --   24.00  75.00 141.94   52
 17  \w      3.00  32.00   0.50    0.08    --   24.00  71.00 158.14   58
 18  \w     13.00  39.00   0.50    0.08    --   32.00  66.00-170.71   52
 19  \w     13.00  39.00   0.50    0.08    --   32.00  66.00 -55.94   52
 20  \w     13.00  39.00   0.50    0.08    --   32.00  66.00  57.09   52
 21  \w     19.00  50.00   0.50    0.08    --   36.00  60.00 -85.60   62
 22  \w     18.00  44.00   0.50    0.08    --   36.00  63.00  -2.22   52
 23  \w     18.00  45.00   0.50    0.08    --   36.00  62.00-133.25   54
 24  \w     18.00  44.00   0.50    0.08    --   36.00  63.00 145.76   52
 25  \w     18.00  45.00   0.50    0.08    --   36.00  62.00  25.97   54
 26  \w    -48.00 -22.00   0.50    0.08    --  -40.00 -61.00  39.56   52
 27  \w     23.00  50.00   0.50    0.08    --   40.00  60.00  91.32   54
 28  \w     32.00 120.00   0.50    0.08    --   46.87  54.00   0.74  176
 29  \w     31.00 120.00   0.50    0.08    --   46.87  55.00 -42.01  178
 30  \w     32.00 120.00   0.50    0.08    --   46.87  54.00  67.53  176
 31  \w   -128.00 -40.00   0.50    0.08    --  -56.00 -55.00 -77.81  176
 32  \w   -128.00 -40.00   0.50    0.08    --  -56.00 -56.00 105.72  176
 33  \w   -132.00 -43.00   0.50    0.08    --  -60.00 -54.00  38.32  178
 34  \w   -132.00 -43.00   0.50    0.08    --  -60.00 -54.00 145.44  178
 35  \w   -132.00 -44.00   0.50    0.08    --  -60.00 -55.00 -47.78  176
 36  \w   -137.00 -48.00   0.50    0.08    --  -64.00 -51.00-170.40  178
 37  \w   -140.00 -53.00   0.50    0.31    --  -68.00 -50.00-118.75  174
 38  \w   -145.00 -55.00   0.50    0.31    --  -72.00 -54.00  94.28  180
 39  \w     56.00 145.00   0.50    0.08    --   72.00  56.00-103.21  178
 40  \w   -149.00 -60.00   0.50    0.31    --  -76.00 -55.00  37.23  178
 41  \w   -149.00 -60.00   0.50    0.31    --  -76.00 -56.00-135.32  178
 42  \w   -153.00 -64.00   0.50    0.31    --  -80.00 -56.00-162.05  178
 43  \w   -153.00 -64.00   0.50    0.31    --  -80.00 -56.00  27.23  178
 44  \w   -153.00 -64.00   0.50    0.31    --  -80.00 -56.00-178.76  178
 45  \w   -153.00 -64.00   0.50    0.31    --  -80.00 -53.00 -14.50  178
 46  \w   -157.00 -67.00   0.50    0.31    --  -84.00 -54.00  13.02  180
 47  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00 112.60  176
 48  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00  89.81  176
 49  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -55.00 142.54  174
 50  \w   -160.00 -78.00   0.50    0.31    --  -88.50 -56.00  66.95  164
 51  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -50.00 -35.41  174
 52  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00   7.37  176
 53  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -55.00 -51.91  174
 54  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00 -14.18  176
 55  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00-107.90  176
 56  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -51.00-170.93  176
 57  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00 160.59  176
 58  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -55.00 126.70  174
 59  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00 -41.32  176
 60  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -53.00 -80.12  174
 61  \w   -160.00 -72.00   0.50    0.31    --  -88.50 -54.00  27.48  176
 62  \w   -160.00 -73.00   0.50    0.31    --  -88.50 -50.00 -98.47  174
 63  \w    -47.00 -16.00   0.50    0.31    --  -88.50  45.00 -60.00   62
 64  \w     80.00 169.00   0.50    0.31    --   96.00  55.00 108.32  178
 65  \w     81.00 170.00   0.50    0.31    --   96.00  40.00 172.00  178
 66  \w     34.00 111.00   0.50    0.31    --  106.69-125.00  60.00  154
 67  \w     91.00 178.00   0.50    0.31    --  106.69  61.00-120.00  174
 68  \w     34.00  76.00   0.50    0.31    --  106.69 -61.00 -60.00   84
 69  \w     34.00  76.00   0.50    0.31    --  106.69 -61.00 -90.00   84
 70  \w     34.00  76.00   0.50    0.31    --  106.69 -61.00 120.00   84
 71  \w    101.00 178.00   0.50    0.31    --  106.69  77.00 -90.00  154
 72  \w     95.00 178.00   0.50    0.31    --  106.69 125.00  90.00  166
 73  \w     95.00 178.00   0.50    0.31    --  106.69 125.00 150.00  166
 74  \w     34.00 100.00   0.50    0.31    --  106.69 -77.00  90.00  132
 75  \w     92.00 178.00   0.50    0.31    --  106.69  45.00-120.00  172
 76  \w     34.00 105.00   0.50    0.31    --  106.69 -94.00  90.00  142
 77  \w     34.00 105.00   0.50    0.31    --  106.69 -94.00-180.00  142
 78  \w     92.00 178.00   0.50    0.31    --  106.69  45.00  30.00  172
 79  \w     35.00  75.00   0.50    0.31    --  106.69 -61.00-180.00   80
 80  \w     94.00 177.00   0.50    0.31    --  106.69  45.00 -30.00  166
;
_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      0.0716227000
_diffrn_orient_matrix_UB_12      -0.0274258000
_diffrn_orient_matrix_UB_13      0.0794103000
_diffrn_orient_matrix_UB_21      0.1006085000
_diffrn_orient_matrix_UB_22      -0.0963226000
_diffrn_orient_matrix_UB_23      -0.0330391000
_diffrn_orient_matrix_UB_31      0.2172868000
_diffrn_orient_matrix_UB_32      0.0895554000
_diffrn_orient_matrix_UB_33      -0.0005882000
_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  0.0412
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            55319
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.609
_diffrn_reflns_theta_min         2.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.042
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.698
_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    1.193
_exptl_crystal_description       plate
_exptl_crystal_F_000             514
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.989
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 4103 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         9686
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0476
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+1.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    0.883
_reflns_Friedel_fraction_max     0.794
_reflns_number_gt                9430
_reflns_number_total             9686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00054k2.cif
_cod_data_source_block           hpd026a
_cod_depositor_comments
'Adding full bibliography for 7159215--7159218.cif.'
_cod_database_code               7159215
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H20O5
_chemical_oxdiff_usercomment     SODXIV-050
_reflns_odcompleteness_completeness 99.96
_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, All O(H) groups
2. Restrained distances
 O9-C45
 1.25 with sigma of 0.02
 H6-O7
 2.25 with sigma of 0.02
 O6-C28
 1.3 with sigma of 0.02
 H6-H43A_$1
 2.2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C28 \\sim C46: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
4. Others
 Fixed Sof: H28(0.25) O6(0.75) H6(0.75) O10(0.75) O9(0.75) H45(0.25)
5.a Ternary CH refined with riding coordinates:
 C36(H36), C32(H32), C14(H14), C15(H15), C5(H5), C9(H9), C41(H41), C42(H42),
 C28(H28)
5.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C13(H13A,H13B), C37(H37A,H37B), C10(H10A,H10B), C16(H16A,
 H16B), C8(H8A,H8B), C34(H34A,H34B), C31(H31A,H31B), C7(H7A,H7B), C40(H40A,
 H40B), C4(H4A,H4B), C17(H17A,H17B), C44(H44A,H44B), C43(H43A,H43B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C39(H39), C45(H45)
5.d Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C), C20(H20A,H20B,
 H20C), C25(H25A,H25B,H25C), C54(H54A,H54B,H54C), C49(H49A,H49B,H49C), C23(H23A,
 H23B,H23C), C26(H26A,H26B,H26C), C19(H19A,H19B,H19C), C47(H47A,H47B,H47C),
 C53(H53A,H53B,H53C), C27(H27A,H27B,H27C), C50(H50A,H50B,H50C), C46(H46A,H46B,
 H46C), C52(H52A,H52B,H52C)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O6(H6)
;
_shelx_res_checksum              3140
_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 1.394
_oxdiff_exptl_absorpt_empirical_full_min 0.782