Concise synthesis of triasteranones from barbaralones.
Yeung, Serena; Allen, Emily G.; Jones, Kieran D.; Argent, Stephen P.; Lam, Hon Wai; Chemical communications (Cambridge, England)  (2026) –; doi:10.1039/d6cc00474a

data_7135657
_publ_section_title
;
 Concise synthesis of triasteranones from barbaralones.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7348
_journal_page_last               7352
_journal_paper_doi               10.1039/d6cc00474a
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C15 H14 O3, C H2 Cl2'
_chemical_formula_sum            'C16 H16 Cl2 O3'
_chemical_formula_weight         327.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-01-12 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.1070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.15220(10)
_cell_length_b                   19.1069(3)
_cell_length_c                   12.9283(2)
_cell_measurement_reflns_used    12918
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.0690
_cell_measurement_theta_min      4.1100
_cell_volume                     1511.09(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 41.123a (release 20-01-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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    -39.00  27.00   1.00    2.00    --  -42.25  57.00-120.00   66
  2  \w    -73.00  30.00   1.00    2.00    --  -42.25  77.00 120.00  103
  3  \w    -95.00 -16.00   1.00    2.00    --  -42.25 -29.00  65.91   79
  4  \w     12.00  40.00   1.00    2.00    --   42.25  77.00-163.40   28
  5  \w     13.00  92.00   1.00    2.00    --   42.25  71.00  89.79   79
  6  \w     17.00  68.00   1.00    2.00    --   42.25  57.00   0.00   51
  7  \w     20.00  45.00   1.00    2.00    --   42.25  57.00-180.00   25
  8  \w     10.00  41.00   1.00    2.00    --   42.25  78.00  -4.19   31
  9  \w     22.00 101.00   1.00    2.00    --   42.25  38.00-120.00   79
 10  \w     17.00  71.00   1.00    2.00    --   42.25  57.00 -60.00   54
 11  \w      6.00  76.00   1.00    2.00    --   42.25 -99.00 -30.00   70
 12  \w     22.00  72.00   1.00    2.00    --   42.25  57.00  30.00   50
 13  \w     52.00  77.00   1.00    2.00    --   42.25  57.00-180.00   25
 14  \w     14.00  39.00   1.00    2.00    --   42.25  78.00-115.35   25
 15  \w     72.00  98.00   1.00    8.00    --  100.82  69.00 -78.74   26
 16  \w     75.00 101.00   1.00    8.00    --  100.82  58.00-109.10   26
 17  \w     75.00 171.00   1.00    8.00    --  100.82  48.00 125.77   96
 18  \w    127.00 172.00   1.00    8.00    --  100.82  69.00-108.69   45
 19  \w     75.00 114.00   1.00    8.00    --  100.82  45.00-180.00   39
 20  \w     72.00  98.00   1.00    8.00    --  100.82  69.00-108.69   26
 21  \w     74.00 167.00   1.00    8.00    --  100.82  61.00  12.55   93
 22  \w     27.00 126.00   1.00    8.00    --  100.82 -77.00  60.00   99
 23  \w     27.00 109.00   1.00    8.00    --  100.82-125.00 -30.00   82
 24  \w    143.00 168.00   1.00    8.00    --  100.82  69.00 119.83   25
 25  \w     31.00  92.00   1.00    8.00    --  100.82 -61.00-180.00   61
 26  \w     77.00 104.00   1.00    8.00    --  100.82  61.00-150.00   27
 27  \w     29.00  57.00   1.00    8.00    --  100.82 -30.00 120.00   28
 28  \w     26.00 110.00   1.00    8.00    --  100.82-116.00  46.00   84
 29  \w     74.00 121.00   1.00    8.00    --  100.82  61.00 -30.00   47
 30  \w     80.00 110.00   1.00    8.00    --  100.82-125.00-120.00   30
 31  \w    138.00 164.00   1.00    8.00    --  100.82  61.00 150.00   26
 32  \w     72.00 159.00   1.00    8.00    --  100.82  67.00 -17.45   87
 33  \w     73.00  99.00   1.00    8.00    --  100.82  69.00 119.83   26
 34  \w    144.00 169.00   1.00    8.00    --  100.82  59.00  82.25   25
 35  \w     74.00 130.00   1.00    8.00    --  100.82  61.00-180.00   56
 36  \w     75.00 102.00   1.00    8.00    --  100.82  59.00  82.25   27
 37  \w     72.00 163.00   1.00    8.00    --  100.82  69.00-133.39   91
 38  \w     74.00 100.00   1.00    8.00    --  100.82  61.00 150.00   26
 39  \w     74.00  99.00   1.00    8.00    --  100.82  61.00  60.00   25
 40  \w     28.00  56.00   1.00    8.00    --  100.82 -30.00-150.00   28
 41  \w     71.00 159.00   1.00    8.00    --  100.82  70.00-171.84   88
 42  \w     75.00 100.00   1.00    8.00    --  100.82  61.00   0.00   25
 43  \w     75.00 113.00   1.00    8.00    --  100.82  52.00 -70.28   38
 44  \w     76.00 107.00   1.00    8.00    --  100.82  45.00 -30.00   31
 45  \w     74.00 101.00   1.00    8.00    --  100.82  61.00  90.00   27
 46  \w     74.00 100.00   1.00    8.00    --  100.82  61.00 120.00   26
 47  \w     57.00  91.00   1.00    8.00    --  100.82 -61.00 -90.00   34
 48  \w     75.00 171.00   1.00    8.00    --  100.82  45.00  60.00   96
 49  \w    124.00 171.00   1.00    8.00    --  100.82  69.00 -78.74   47
 50  \w     71.00  98.00   1.00    8.00    --  100.82  70.00  11.47   27
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku OD SuperNova GV1000 Titan S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.2481685000
_diffrn_orient_matrix_UB_12      0.0002515000
_diffrn_orient_matrix_UB_13      0.0076987000
_diffrn_orient_matrix_UB_21      0.0058524000
_diffrn_orient_matrix_UB_22      -0.0796273000
_diffrn_orient_matrix_UB_23      0.0187028000
_diffrn_orient_matrix_UB_31      0.0422999000
_diffrn_orient_matrix_UB_32      0.0126318000
_diffrn_orient_matrix_UB_33      0.1181354000
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            23557
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.076
_diffrn_reflns_theta_min         4.145
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.929
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.720
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.63a (Rigaku Oxford Diffraction, 2023)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-heptane, dichloromethane'
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.899
_refine_diff_density_min         -0.570
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     206
_refine_ls_number_reflns         2948
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0391
_refine_ls_R_factor_gt           0.0367
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0394P)^2^+1.2217P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0902
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2747
_reflns_number_total             2948
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00474a2.cif
_cod_data_source_block           syhwlg
_cod_depositor_comments
'Adding full bibliography for 7135655--7135659.cif.'
_cod_database_code               7135657
_nottingham_internal_coll_name   SYHWLG
_nottingham_internal_coll_number 20019
_nottingham_internal_coll_client SY/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '8.00, 2.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   30/01/2025
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 07/02/2025
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 07/02/2025
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 07/02/2025
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 07/02/2025
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 07/02/2025
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C15H14O3
_chemical_oxdiff_usercomment
'SYHWLG #20019 GVA-2223 SY/HWL fomblin oil on micromount '
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.452
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O11-H11 = O10-H10
 0.84 with sigma of 0.02
 C1S-Cl3S \\sim C1S-Cl3T
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl3T \\sim Cl3S: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
4. Rigid body (RIGU) restrains
 Cl3S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H1SC)=Sof(H1SD)=Sof(Cl3T)=1-FVAR(1)
 Sof(H1SA)=Sof(H1SB)=Sof(Cl3S)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9)
6.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1S(H1SC,H1SD)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18)
;
_shelx_res_checksum              39231
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.810