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_7160722
_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 H30 O3'
_chemical_formula_sum            'C19 H30 O3'
_chemical_formula_weight         306.43
_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                   7.59870(10)
_cell_length_b                   12.27340(10)
_cell_length_c                   17.7907(2)
_cell_measurement_reflns_used    12310
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2090
_cell_measurement_theta_min      4.3800
_cell_volume                     1659.19(3)
_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 0.999
_diffrn_measured_fraction_theta_max 0.974
_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    101.00 178.00   0.50    1.75    --  106.91  88.00 137.00  154
  2  \w     34.00  71.00   0.50    1.75    --  106.91 -61.00   0.00   74
  3  \w     34.00 101.00   0.50    1.75    --  106.91 -77.00 -30.00  134
  4  \w     34.00 101.00   0.50    1.75    --  106.91 -77.00 -30.00  134
  5  \w     34.00  71.00   0.50    1.75    --  106.91 -61.00 -90.00   74
  6  \w     34.00  71.00   0.50    1.75    --  106.91 -61.00-180.00   74
  7  \w     34.00  71.00   0.50    1.75    --  106.91 -61.00  30.00   74
  8  \w     32.00  77.00   0.50    0.44    --   46.90  37.00 120.00   90
  9  \w     83.00 119.00   0.50    0.44    --   46.90  57.00 150.00   72
 10  \w     83.00 119.00   0.50    0.44    --   46.90  57.00 120.00   72
 11  \w     32.00 121.00   0.50    0.44    --   46.90  37.00  30.00  178
 12  \w     83.00 119.00   0.50    0.44    --   46.90  57.00-180.00   72
 13  \w    -43.00  27.00   0.50    0.44    --  -46.90  37.00 -49.00  140
 14  \w    -51.00 -19.00   0.50    1.75    --  -91.75  45.00   0.00   64
 15  \w    -82.00  -2.00   0.50    0.44    --  -46.90 111.00  30.00  160
 16  \w     38.00 108.00   0.50    1.75    --  106.91-111.00 -62.00  140
 17  \w     34.00 106.00   0.50    1.75    --  106.91 -94.00 -30.00  144
 18  \w   -119.00 -83.00   0.50    0.44    --  -46.90 -57.00  30.00   72
 19  \w   -119.00 -83.00   0.50    0.44    --  -46.90 -57.00 -30.00   72
 20  \w   -119.00 -83.00   0.50    0.44    --  -46.90 -57.00 -60.00   72
 21  \w   -164.00-100.00   0.50    1.75    --  -91.75 -94.00  90.00  128
 22  \w   -164.00 -91.00   0.50    1.75    --  -91.75 -61.00 120.00  146
 23  \w   -166.00 -77.00   0.50    1.75    --  -91.75 -37.00 154.00  178
 24  \w   -164.00 -77.00   0.50    1.75    --  -91.75 -45.00-120.00  174
;
_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      -0.0337393000
_diffrn_orient_matrix_UB_12      0.0359934000
_diffrn_orient_matrix_UB_13      -0.0816995000
_diffrn_orient_matrix_UB_21      -0.1798621000
_diffrn_orient_matrix_UB_22      0.0470906000
_diffrn_orient_matrix_UB_23      0.0233947000
_diffrn_orient_matrix_UB_31      0.0873034000
_diffrn_orient_matrix_UB_32      0.1106173000
_diffrn_orient_matrix_UB_33      0.0166723000
_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  0.0353
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            15752
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.621
_diffrn_reflns_theta_min         4.376
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.636
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.883
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       plate
_exptl_crystal_F_000             672
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1306 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.10(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     204
_refine_ls_number_reflns         3350
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0314
_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^)+(0.0496P)^2^+0.2296P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0848
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.924
_reflns_number_gt                3224
_reflns_number_total             3350
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01218j2.cif
_cod_data_source_block           hpd919_auto
_cod_depositor_comments
'Adding full bibliography for 7160722--7160727.cif.'
_cod_database_code               7160722
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     AEIII-063
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.945
_diffrn_oxdiff_digest_hkl
;
018d189eacf42b23de1b1c553e55d7fba7d82b
;
_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.a Ternary CH refined with riding coordinates:
 C9(H9), C14(H14), C8(H8), C17(H17), C3(H3A), C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C7(H7A,H7B), C6(H6A,H6B), C15(H15A,H15B), C2(H2A,H2B),
 C11(H11A,H11B), 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)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3(H3), O2(H2)
;
_shelx_res_checksum              43678
_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 1.315
_oxdiff_exptl_absorpt_empirical_full_min 0.839