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_7160727
_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 H43 O3 Si'
_chemical_formula_sum            'C25 H43 O3 Si'
_chemical_formula_weight         419.68
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.22960(10)
_cell_length_b                   11.0072(2)
_cell_length_c                   30.5982(5)
_cell_measurement_reflns_used    10247
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      75.4760
_cell_measurement_theta_min      2.9100
_cell_volume                     2434.93(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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 2018/2 (Sheldrick, 2018)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.961
_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   -119.00 -31.00   0.50    0.86    --  -46.90 -53.00  31.00  176
  2  \w    -60.00 -19.00   0.50    3.43    --  -91.75  53.00 175.00   82
  3  \w   -164.00 -71.00   0.50    3.43    --  -91.75 -68.00-157.00  186
  4  \w     34.00  82.00   0.50    3.43    --  106.91 -68.00-157.00   96
  5  \w     49.00 132.00   0.50    3.43    --  106.91-154.00 165.00  166
  6  \w    -30.00  29.00   0.50    0.86    --  -46.90  19.00 -30.00  118
  7  \w   -119.00 -83.00   0.50    0.86    --  -46.90 -57.00 -60.00   72
  8  \w     83.00 119.00   0.50    0.86    --   46.90  57.00-150.00   72
  9  \w   -164.00 -91.00   0.50    3.43    --  -91.75 -61.00 120.00  146
 10  \w   -162.00 -87.00   0.50    3.43    --  -91.75-125.00-180.00  150
 11  \w    -51.00 -19.00   0.50    3.43    --  -91.75  45.00 -90.00   64
 12  \w    -51.00 -19.00   0.50    3.43    --  -91.75  45.00 -60.00   64
 13  \w     34.00 101.00   0.50    3.43    --  106.91 -77.00   0.00  134
 14  \w     34.00  71.00   0.50    3.43    --  106.91 -61.00 -90.00   74
 15  \w     34.00  60.00   0.50    3.43    --  106.91 -53.00  31.00   52
 16  \w     34.00  71.00   0.50    3.43    --  106.91 -61.00   0.00   74
 17  \w     95.00 177.00   0.50    3.43    --  106.91 125.00  90.00  164
 18  \w   -119.00 -83.00   0.50    0.86    --  -46.90 -57.00   0.00   72
 19  \w   -119.00 -83.00   0.50    0.86    --  -46.90 -57.00 -30.00   72
 20  \w     32.00 121.00   0.50    0.86    --   46.90  37.00 -90.00  178
 21  \w     32.00 119.00   0.50    0.86    --   46.90  53.00 175.00  174
 22  \w   -164.00-139.00   0.50    3.43    --  -91.75 -45.00 -90.00   50
 23  \w   -164.00 -76.00   0.50    3.43    --  -91.75 -53.00  31.00  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      -0.0313581000
_diffrn_orient_matrix_UB_12      -0.0009951000
_diffrn_orient_matrix_UB_13      -0.0498039000
_diffrn_orient_matrix_UB_21      0.1334496000
_diffrn_orient_matrix_UB_22      -0.1084420000
_diffrn_orient_matrix_UB_23      -0.0043948000
_diffrn_orient_matrix_UB_31      -0.1631632000
_diffrn_orient_matrix_UB_32      -0.0884340000
_diffrn_orient_matrix_UB_33      0.0059827000
_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  0.0769
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            21739
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.212
_diffrn_reflns_theta_min         2.888
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.012
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.145
_exptl_crystal_description       plate
_exptl_crystal_F_000             924
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.094
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.341
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1656 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         4811
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0400P)^2^+1.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1350
_refine_ls_wR_factor_ref         0.1370
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.920
_reflns_number_gt                4455
_reflns_number_total             4811
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01218j2.cif
_cod_data_source_block           hpd871c
_cod_depositor_comments
'Adding full bibliography for 7160722--7160727.cif.'
_cod_database_code               7160727
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O Si'
_chemical_oxdiff_usercomment     'Acurest mono TBOM S'
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.911
_diffrn_oxdiff_digest_hkl
;
01ace214e5375497832a6841f4aa8a0e48e3d8
;
_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 C(H,H,H,H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C22B) = Uanis(C25B) = Uanis(Si1B) = Uanis(C26B) = Uanis(C20B)
3. Others
 Fixed Sof: Si1A(0.7) Si1B(0.3) O1A(0.75) H1A(0.75) H21A(0.7) H21B(0.7)
 H21C(0.7) H21D(0.3) H21E(0.3) H21F(0.3) C25A(0.7) H25A(0.7) H25B(0.7)
 H25C(0.7) C20A(0.7) H20A(0.7) H20B(0.7) H20C(0.7) C23A(0.7) H23A(0.7)
 H23B(0.7) H23C(0.7) C24A(0.7) H24A(0.7) H24B(0.7) H24C(0.7) C22A(0.7)
 C25B(0.3) H25D(0.3) H25E(0.3) H25F(0.3) C22B(0.3) C23B(0.3) H23D(0.3)
 H23E(0.3) H23F(0.3) C20B(0.3) H20D(0.3) H20E(0.3) H20F(0.3) C26B(0.3)
 H26A(0.3) H26B(0.3) H26C(0.3) O1B(0.25) H1B(0.25)
4.a Ternary CH refined with riding coordinates:
 C9(H9), C8(H8), C14(H14), C3(H3), C1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C7(H7A,H7B), C16(H16A,H16B), C6(H6A,H6B),
 C2(H2A,H2B), C15(H15A,H15B)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4)
4.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C21(H21D,H21E,
 H21F), C25A(H25A,H25B,H25C), C20A(H20A,H20B,H20C), C23A(H23A,H23B,H23C),
 C24A(H24A,H24B,H24C), C25B(H25D,H25E,H25F), C23B(H23D,H23E,H23F), C20B(H20D,
 H20E,H20F), C26B(H26A,H26B,H26C)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O1A(H1A), O1B(H1B)
;
_shelx_res_checksum              83098
_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 2.219
_oxdiff_exptl_absorpt_empirical_full_min 0.474