A synthesis of 1β-hydroxytestosterone, a metabolite of xenobiotic human cytochrome P450 enzymes, beginning with a borylation of boldione.
Elizondo, Anna I.; McCarty, Kevin D.; Arman, Hadi D.; Guengerich, F. Peter; Yoshimoto, Francis K.; Organic & biomolecular chemistry 23 (2025) 9618–9623; doi:10.1039/d5ob01218j

data_7160726
_publ_section_title
;
 A synthesis of 1&#x3b2;-hydroxytestosterone, a metabolite of xenobiotic
 human cytochrome P450 enzymes, beginning with a borylation of boldione.
;
_journal_issue                   42
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9618
_journal_page_last               9623
_journal_paper_doi               10.1039/d5ob01218j
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H40 O3 Si'
_chemical_formula_sum            'C25 H40 O3 Si'
_chemical_formula_weight         416.66
_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   geom
_audit_creation_date             2025-05-01
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-02 deposited with the CCDC.	2025-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.961(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.3196(5)
_cell_length_b                   7.2773(2)
_cell_length_c                   15.2503(6)
_cell_measurement_reflns_used    4568
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.5650
_cell_measurement_theta_min      3.0970
_cell_volume                     1173.13(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.126a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.126a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.126a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 0.997
_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     34.00  71.00   0.50    0.05    --  106.91 -61.00 -90.00   74
  2  \w     34.00 101.00   0.50    0.05    --  106.91 -77.00 -90.00  134
  3  \w     34.00 101.00   0.50    0.05    --  106.91 -77.00 -30.00  134
  4  \w     34.00  71.00   0.50    0.05    --  106.91 -61.00  30.00   74
  5  \w     34.00  71.00   0.50    0.05    --  106.91 -61.00  90.00   74
  6  \w     34.00  71.00   0.50    0.05    --  106.91 -61.00 150.00   74
  7  \w    -28.00  43.00   0.50    0.05    --   45.59 -37.00  47.00  142
  8  \w    101.00 178.00   0.50    0.05    --  106.91  88.00  29.00  154
  9  \w     92.00 178.00   0.50    0.05    --  106.91  37.00-156.00  172
 10  \w     31.00 120.00   0.50    0.05    --   45.59  37.00-156.00  178
 11  \w    -43.00  28.00   0.50    0.05    --  -45.59  37.00-156.00  142
 12  \w    -51.00 -19.00   0.50    0.05    --  -91.75  45.00-120.00   64
 13  \w    -85.00 -22.00   0.50    0.05    --  -91.75 125.00 -60.00  126
 14  \w    -51.00 -19.00   0.50    0.05    --  -91.75  45.00  30.00   64
 15  \w    -43.00  28.00   0.50    0.05    --  -45.59  37.00 -30.00  142
 16  \w   -166.00 -76.00   0.50    0.05    --  -91.75 -30.00 -30.00  180
 17  \w   -166.00 -76.00   0.50    0.05    --  -91.75 -30.00 -30.00  180
 18  \w   -117.00 -83.00   0.50    0.05    --  -45.59 -57.00  60.00   68
 19  \w   -117.00 -83.00   0.50    0.05    --  -45.59 -57.00  90.00   68
 20  \w   -164.00-101.00   0.50    0.05    --  -91.75 -77.00   0.00  126
 21  \w   -161.00 -81.00   0.50    0.05    --  -91.75-113.00-170.00  160
 22  \w   -161.00 -81.00   0.50    0.05    --  -91.75-113.00-170.00  160
 23  \w    -65.00 -39.00   0.50    0.05    --  -46.90 113.00 -78.00   52
 24  \w   -118.00 -91.00   0.50    0.05    --  -46.90 -57.00 -90.00   54
 25  \w    -70.00 -28.00   0.50    0.05    --  -46.90  77.00 -90.00   84
 26  \w     -9.00  18.00   0.50    0.05    --  -46.90  77.00 -90.00   54
 27  \w     83.00 108.00   0.50    0.05    --   46.90  57.00 -90.00   50
 28  \w   -164.00 -92.00   0.50    0.05    --  -91.75 -61.00  90.00  144
 29  \w   -162.00-136.00   0.50    0.05    --  -91.75 -61.00 120.00   52
 30  \w    -47.00 -20.00   0.50    0.05    --  -91.75  61.00  30.00   54
 31  \w    -48.00 -22.00   0.50    0.05    --  -91.75  45.00 -90.00   52
 32  \w   -133.00-101.00   0.50    0.05    --  -91.75 -61.00 120.00   64
 33  \w    -84.00 -34.00   0.50    0.05    --  -91.75 125.00 150.00  100
 34  \w   -141.00-115.00   0.50    0.05    --  -91.75 -77.00  60.00   52
 35  \w     39.00  65.00   0.50    0.05    --  106.91-125.00  30.00   52
 36  \w     51.00 101.00   0.50    0.05    --  106.91 -77.00-150.00  100
 37  \w     87.00 112.00   0.50    0.05    --  106.91-125.00  30.00   50
 38  \w     86.00 112.00   0.50    0.05    --  106.91-125.00 -30.00   52
 39  \w     73.00 112.00   0.50    0.05    --  106.91-125.00-180.00   78
 40  \w     86.00 112.00   0.50    0.05    --  106.91-125.00  60.00   52
 41  \w     42.00  68.00   0.50    0.05    --  106.91-125.00  60.00   52
 42  \w     74.00 100.00   0.50    0.05    --  106.91 -94.00  60.00   52
 43  \w     84.00 110.00   0.50    0.05    --  106.91-125.00 150.00   52
 44  \w     42.00  74.00   0.50    0.05    --  106.91-125.00 150.00   64
 45  \w     72.00 103.00   0.50    0.05    --  106.91 -94.00-150.00   62
 46  \w     83.00 108.00   0.50    0.05    --  106.91-113.00-170.00   50
 47  \w     39.00  75.00   0.50    0.05    --  106.91-113.00-170.00   72
;
_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      0.0763259000
_diffrn_orient_matrix_UB_12      0.0582250000
_diffrn_orient_matrix_UB_13      -0.0611733000
_diffrn_orient_matrix_UB_21      -0.1035595000
_diffrn_orient_matrix_UB_22      -0.0809195000
_diffrn_orient_matrix_UB_23      -0.0872131000
_diffrn_orient_matrix_UB_31      -0.0685035000
_diffrn_orient_matrix_UB_32      0.1868089000
_diffrn_orient_matrix_UB_33      -0.0187054000
_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  0.0649
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16148
_diffrn_reflns_point_group_measured_fraction_full 0.841
_diffrn_reflns_point_group_measured_fraction_max 0.788
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.537
_diffrn_reflns_theta_min         3.103
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.049
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.714
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.126a (Rigaku Oxford Diffraction, 2024)
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 dark colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.180
_exptl_crystal_description       plate
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.375
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 1069 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         3885
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0424
_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^)+(0.0574P)^2^+0.1258P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1027
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.513
_reflns_Friedel_fraction_full    0.655
_reflns_Friedel_fraction_max     0.582
_reflns_number_gt                3450
_reflns_number_total             3885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01218j2.cif
_cod_data_source_block           hpd914_auto
_cod_depositor_comments
'Adding full bibliography for 7160722--7160727.cif.'
_cod_database_code               7160726
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O Si'
_chemical_oxdiff_usercomment     AEIII-042
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.797
_diffrn_oxdiff_digest_hkl
;
01a779115c6c9a089af1bb454fadd0c7896bd0
;
_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:
 C14(H14), C8(H8), C3(H3), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C7(H7A,H7B), C2(H2A,H2B), C6(H6A,H6B), C11(H11A,H11B),
 C15(H15A,H15B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C25(H25A,H25B,H25C), C21(H21A,H21B,
 H21C), C24(H24A,H24B,H24C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              59965
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.822