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_7160723
_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         'C19 H28 O3'
_chemical_formula_sum            'C19 H28 O3'
_chemical_formula_weight         304.41
_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
_audit_creation_date             2025-05-01
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-05-02 deposited with the CCDC.	2025-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.743(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.1137(6)
_cell_length_b                   6.2606(2)
_cell_length_c                   13.1134(7)
_cell_measurement_reflns_used    4680
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      73.5780
_cell_measurement_theta_min      3.6390
_cell_volume                     828.65(8)
_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      100.01(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.949
_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 -30.00   0.50    3.00    --  -46.89 -54.00 -86.00  178
  2  \w    -62.00  26.00   0.50    3.00    --  -46.89  54.00  56.00  176
  3  \w    -25.00  63.00   0.50    3.00    --   46.89 -54.00 -86.00  176
  4  \w    -62.00 -19.00   0.50   12.00    --  -91.75  54.00  56.00   86
  5  \w   -164.00 -75.00   0.50   12.00    --  -91.75 -54.00 -86.00  178
  6  \w     91.00 178.00   0.50   12.00    --  106.92  54.00  56.00  174
  7  \w     34.00  62.00   0.50   12.00    --  106.92 -54.00 -86.00   56
  8  \w     32.00 119.00   0.50    3.00    --   46.89  54.00  56.00  174
  9  \w     83.00 119.00   0.50    3.00    --   46.89  57.00-120.00   72
 10  \w     34.00  94.00   0.50    3.00    --   46.89-125.00 120.00  120
 11  \w    -71.00 -19.00   0.50   12.00    --  -91.75  61.00 150.00  104
 12  \w    -51.00 -19.00   0.50   12.00    --  -91.75  45.00-150.00   64
 13  \w    -85.00 -22.00   0.50   12.00    --  -91.75 125.00 -30.00  126
 14  \w    -51.00 -19.00   0.50   12.00    --  -91.75  45.00-120.00   64
 15  \w   -164.00-101.00   0.50   12.00    --  -91.75 -77.00-150.00  126
 16  \w    -51.00 -19.00   0.50   12.00    --  -91.75  45.00 150.00   64
 17  \w    -51.00 -19.00   0.50   12.00    --  -91.75  45.00-180.00   64
 18  \w    -71.00 -19.00   0.50   12.00    --  -91.75  61.00   0.00  104
 19  \w     34.00  71.00   0.50   12.00    --  106.92 -61.00  60.00   74
 20  \w     34.00 106.00   0.50   12.00    --  106.92 -94.00-120.00  144
 21  \w     34.00 106.00   0.50   12.00    --  106.92 -94.00 -90.00  144
 22  \w     91.00 178.00   0.50   12.00    --  106.92  61.00 -30.00  174
 23  \w     34.00  71.00   0.50   12.00    --  106.92 -61.00  30.00   74
 24  \w     34.00  71.00   0.50   12.00    --  106.92 -61.00 150.00   74
 25  \w   -121.00 -32.00   0.50    3.00    --  -46.89 -37.00  60.00  178
 26  \w   -121.00 -32.00   0.50    3.00    --  -46.89 -37.00 -30.00  178
 27  \w   -121.00 -66.00   0.50    3.00    --  -46.89 -37.00-180.00  110
 28  \w   -121.00 -32.00   0.50    3.00    --  -46.89 -37.00 150.00  178
;
_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      0.0662496000
_diffrn_orient_matrix_UB_12      0.0196840000
_diffrn_orient_matrix_UB_13      -0.0819280000
_diffrn_orient_matrix_UB_21      0.0157448000
_diffrn_orient_matrix_UB_22      0.2423643000
_diffrn_orient_matrix_UB_23      0.0220916000
_diffrn_orient_matrix_UB_31      0.1365561000
_diffrn_orient_matrix_UB_32      -0.0375810000
_diffrn_orient_matrix_UB_33      0.0976674000
_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  0.1223
_diffrn_reflns_av_unetI/netI     0.0717
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9081
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.983
_diffrn_reflns_theta_min         3.711
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.637
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85877
_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    1.220
_exptl_crystal_description       plank
_exptl_crystal_F_000             332
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 1053 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.2(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     207
_refine_ls_number_reflns         2879
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0658
_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^)+(0.0300P)^2^+1.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1427
_refine_ls_wR_factor_ref         0.1445
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_full    0.899
_reflns_Friedel_fraction_max     0.873
_reflns_number_gt                2733
_reflns_number_total             2879
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 178.1918\% 
around [0.90 -0.00 -0.44] (reciprocal) or [1.00 -0.01 -0.00] (direct)
;
_cod_data_source_file            d5ob01218j2.cif
_cod_data_source_block           hpd813c_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 7160722--7160727.cif.'
_cod_database_code               7160723
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     AEI-081C
_diffrn_oxdiff_digest_hkl
;
01dc008d8b3f7cf12073abae4d66ead7862e32
;
_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) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C1(H1), C8(H8), C9(H9), C17(H17)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C2(H2A,H2B), C7(H7A,H7B), C11(H11A,H11B), C15(H15A,H15B),
 C12(H12A,H12B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              57490
_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 1.358
_oxdiff_exptl_absorpt_empirical_full_min 0.747
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2