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_7160725
_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, H2 O'
_chemical_formula_sum            'C19 H32 O4'
_chemical_formula_weight         324.44
_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   mixed
_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                   7.94675(7)
_cell_length_b                   9.36032(10)
_cell_length_c                   23.0080(3)
_cell_measurement_reflns_used    11543
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4340
_cell_measurement_theta_min      3.8420
_cell_volume                     1711.43(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 0.969
_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   -162.00 -68.00   0.50    0.11    --  -91.75-133.00  -3.00  188
  2  \w   -162.00 -68.00   0.50    0.11    --  -91.75-133.00  -3.00  188
  3  \w   -119.00 -83.00   0.50    0.05    --  -46.90 -57.00 -90.00   72
  4  \w   -119.00 -83.00   0.50    0.05    --  -46.90 -57.00   0.00   72
  5  \w   -119.00 -83.00   0.50    0.05    --  -46.90 -57.00  60.00   72
  6  \w    -85.00 -22.00   0.50    0.11    --  -91.75 125.00-150.00  126
  7  \w    -92.00 -17.00   0.50    0.05    --  -46.90 133.00  65.00  150
  8  \w    -51.00 -19.00   0.50    0.11    --  -91.75  45.00 -30.00   64
  9  \w    -46.00 -18.00   0.50    0.11    --  -91.75  40.00  16.00   56
 10  \w    -51.00 -19.00   0.50    0.11    --  -91.75  45.00  30.00   64
 11  \w    -51.00 -19.00   0.50    0.11    --  -91.75  45.00  90.00   64
 12  \w    -51.00 -19.00   0.50    0.11    --  -91.75  45.00 120.00   64
 13  \w    -46.00  27.00   0.50    0.05    --  -46.90  40.00  16.00  146
 14  \w    101.00 178.00   0.50    0.11    --  106.91  80.00-177.00  154
 15  \w     32.00  85.00   0.50    0.05    --   46.90  37.00  60.00  106
 16  \w     93.00 178.00   0.50    0.11    --  106.91  45.00 150.00  170
 17  \w     93.00 178.00   0.50    0.11    --  106.91  45.00 150.00  170
 18  \w     92.00 178.00   0.50    0.11    --  106.91  30.00  90.00  172
 19  \w     95.00 177.00   0.50    0.11    --  106.91 125.00 -90.00  164
 20  \w     95.00 177.00   0.50    0.11    --  106.91 125.00 -90.00  164
 21  \w     34.00  71.00   0.50    0.11    --  106.91 -61.00-150.00   74
 22  \w     34.00 101.00   0.50    0.11    --  106.91 -77.00 120.00  134
;
_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      0.0490318000
_diffrn_orient_matrix_UB_12      -0.0729834000
_diffrn_orient_matrix_UB_13      0.0576084000
_diffrn_orient_matrix_UB_21      -0.0867069000
_diffrn_orient_matrix_UB_22      0.1209865000
_diffrn_orient_matrix_UB_23      0.0341828000
_diffrn_orient_matrix_UB_31      -0.1661793000
_diffrn_orient_matrix_UB_32      -0.0844233000
_diffrn_orient_matrix_UB_33      -0.0009132000
_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  0.0350
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            16382
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.612
_diffrn_reflns_theta_min         3.842
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.688
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.683
_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    1.259
_exptl_crystal_description       plank
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.118
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.151
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1345 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(8)
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         3410
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0281
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0404P)^2^+0.3755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0734
_refine_ls_wR_factor_ref         0.0739
_reflns_Friedel_coverage         0.691
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                3326
_reflns_number_total             3410
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01218j2.cif
_cod_data_source_block           hpd913_auto
_cod_depositor_comments
'Adding full bibliography for 7160722--7160727.cif.'
_cod_database_code               7160725
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O'
_chemical_oxdiff_usercomment     AEIII-036b
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.923
_diffrn_oxdiff_digest_hkl
;
012d8066ad746781373eb3ae7e21174117f4ab
;
_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), C8(H8), C14(H14), C1(H1A), C17(H17), C3(H3A)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C15(H15A,H15B), C7(H7A,H7B), C2(H2A,H2B), C11(H11A,H11B),
 C16(H16A,H16B), C6(H6A,H6B)
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              9588
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.836