Enantioselective <i>de novo</i> synthesis of 14-hydroxy-6-oxomorphinans.
Moore, Jonathan C.; Modell, Louis; Glenn, Jacqueline R.; Jones, Kieran D.; Argent, Stephen P.; Lane, J. Robert; Canals, Meritxell; Lam, Hon Wai; Chemical communications (Cambridge, England) 60 (2024) 6007–6010; doi:10.1039/d4cc01788a

data_7133038
_publ_section_title
;
 Enantioselective <i>de novo</i> synthesis of 14-hydroxy-6-oxomorphinans.
;
_journal_issue                   47
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6007
_journal_page_last               6010
_journal_paper_doi               10.1039/d4cc01788a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H28 F3 N O8 S'
_chemical_formula_sum            'C23 H28 F3 N O8 S'
_chemical_formula_weight         535.52
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-04-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-03-19 deposited with the CCDC.	2024-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.773(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0308(2)
_cell_length_b                   11.67240(10)
_cell_length_c                   11.0847(2)
_cell_measurement_reflns_used    17249
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.6210
_cell_measurement_theta_min      4.4660
_cell_volume                     1274.22(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_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 1.000
_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    -20.00  27.00   1.00    3.00    --  -43.06  38.00-180.00   47
  2  \w    -69.00  26.00   1.00    3.00    --  -43.06  77.00  60.00   95
  3  \w     16.00  43.00   1.00    3.00    --   43.06  66.00 -15.22   27
  4  \w     68.00  97.00   1.00    3.00    --   43.06  57.00 -60.00   29
  5  \w     13.00  39.00   1.00    3.00    --   43.06  77.00-159.07   26
  6  \w     27.00  78.00   1.00    3.00    --   43.06  57.00-120.00   51
  7  \w     63.00  94.00   1.00    3.00    --   43.06  38.00  60.00   31
  8  \w    -26.00  67.00   1.00    3.00    --   43.06 -57.00-120.00   93
  9  \w     19.00  96.00   1.00    3.00    --   43.06  57.00  90.00   77
 10  \w     21.00  71.00   1.00    3.00    --   43.06  67.00  20.17   50
 11  \w     55.00  98.00   1.00    3.00    --   43.06  57.00-180.00   43
 12  \w     21.00  66.00   1.00    3.00    --   43.06  57.00 -60.00   45
 13  \w     19.00  46.00   1.00    3.00    --   43.06  57.00-180.00   27
 14  \w     23.00  61.00   1.00    3.00    --   43.06  38.00  60.00   38
 15  \w     13.00  39.00   1.00    3.00    --   43.06  76.00 128.52   26
 16  \w     72.00 170.00   1.00   12.00    --  100.81  71.00 158.77   98
 17  \w     75.00 105.00   1.00   12.00    --  100.81  63.00 -72.76   30
 18  \w     77.00 102.00   1.00   12.00    --  100.81  59.00 142.45   25
 19  \w     78.00 169.00   1.00   12.00    --  100.81  57.00 129.15   91
 20  \w     33.00  93.00   1.00   12.00    --  100.81 -61.00  60.00   60
 21  \w    130.00 170.00   1.00   12.00    --  100.81  64.00-160.47   40
 22  \w    133.00 169.00   1.00   12.00    --  100.81  59.00  52.59   36
 23  \w     76.00 103.00   1.00   12.00    --  100.81  61.00 150.00   27
 24  \w     76.00 102.00   1.00   12.00    --  100.81  61.00 -30.00   26
 25  \w     76.00 170.00   1.00   12.00    --  100.81  61.00 -90.00   94
 26  \w     29.00  71.00   1.00   12.00    --  100.81 -77.00 150.00   42
 27  \w     97.00 124.00   1.00   12.00    --  100.81 -77.00 150.00   27
 28  \w     81.00 110.00   1.00   12.00    --  100.81  45.00   0.00   29
 29  \w    137.00 170.00   1.00   12.00    --  100.81  61.00-180.00   33
 30  \w     72.00 107.00   1.00   12.00    --  100.81-125.00 120.00   35
 31  \w     75.00 101.00   1.00   12.00    --  100.81  64.00-160.47   26
 32  \w     29.00 127.00   1.00   12.00    --  100.81 -77.00 -60.00   98
 33  \w     30.00 113.00   1.00   12.00    --  100.81-125.00-120.00   83
 34  \w    128.00 158.00   1.00   12.00    --  100.81  54.00 120.82   30
 35  \w     76.00 103.00   1.00   12.00    --  100.81  59.00  52.59   27
 36  \w     76.00 103.00   1.00   12.00    --  100.81  61.00  30.00   27
 37  \w     76.00 125.00   1.00   12.00    --  100.81  61.00  90.00   49
 38  \w     78.00 109.00   1.00   12.00    --  100.81  61.00  68.58   31
 39  \w    127.00 166.00   1.00   12.00    --  100.81  61.00  30.00   39
 40  \w     77.00 123.00   1.00   12.00    --  100.81  54.00 120.82   46
 41  \w     76.00 108.00   1.00   12.00    --  100.81  61.00   0.00   32
 42  \w     76.00 102.00   1.00   12.00    --  100.81  61.00-180.00   26
 43  \w     29.00 106.00   1.00   12.00    --  100.81-125.00 -30.00   77
 44  \w     77.00 102.00   1.00   12.00    --  100.81  61.00-120.00   25
 45  \w     78.00 105.00   1.00   12.00    --  100.81  48.00-148.68   27
 46  \w     76.00 102.00   1.00   12.00    --  100.81  61.00 -60.00   26
 47  \w     81.00 158.00   1.00   12.00    --  100.81  45.00 -30.00   77
 48  \w     79.00 111.00   1.00   12.00    --  100.81  45.00-120.00   32
 49  \w     54.00  80.00   1.00   12.00    --  100.81-125.00  30.00   26
 50  \w     88.00 113.00   1.00   12.00    --  100.81-125.00  30.00   25
 51  \w     73.00 150.00   1.00   12.00    --  100.81  68.00-110.87   77
 52  \w     73.00 170.00   1.00   12.00    --  100.81  70.00   5.06   97
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, 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      -0.0409812000
_diffrn_orient_matrix_UB_12      -0.1245226000
_diffrn_orient_matrix_UB_13      -0.0466926000
_diffrn_orient_matrix_UB_21      0.1187548000
_diffrn_orient_matrix_UB_22      -0.0093905000
_diffrn_orient_matrix_UB_23      -0.0367308000
_diffrn_orient_matrix_UB_31      0.0932206000
_diffrn_orient_matrix_UB_32      -0.0426647000
_diffrn_orient_matrix_UB_33      0.1438859000
_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  0.0211
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21190
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.736
_diffrn_reflns_theta_min         4.468
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.751
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.755
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
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    1.396
_exptl_crystal_description       plate
_exptl_crystal_F_000             560
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: EtOAc and pentane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 2289 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         4978
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0216
_refine_ls_R_factor_gt           0.0215
_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^)+(0.0346P)^2^+0.2029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0564
_refine_ls_wR_factor_ref         0.0565
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                4947
_reflns_number_total             4978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01788a2.cif
_cod_data_source_block           jmhwlc
_cod_depositor_comments
'Adding full bibliography for 7133037--7133039.cif.'
_cod_database_code               7133038
_nottingham_internal_coll_name   JMHWLC
_nottingham_internal_coll_number 19434
_nottingham_internal_coll_client JM/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '12.00, 3.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczkj1
_nottingham_internal_coll_date   25/04/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 26/04/2023
_nottingham_internal_process_user pczkj1
_nottingham_internal_solution_date 26/04/2023
_nottingham_internal_solution_user pczkj1
_nottingham_internal_refinement_date 26/04/2023
_nottingham_internal_refinement_user pczkj1
_nottingham_internal_self_archive_date 26/04/2023
_nottingham_internal_validation_date pczspa
_nottingham_internal_validation_user 26/04/2023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H28F3NO8S
_chemical_oxdiff_usercomment
'JMHWLC #19434 GVA-2056 KDJ/HWL fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.721
_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. Restrained distances
 O1-H1
 0.84 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C1(H1A)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C18(H18), C20(H20), C21(H21)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C22(H22A,H22B,
 H22C)
;
_shelx_res_checksum              50425
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id JMHWLC
_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 1.276
_oxdiff_exptl_absorpt_empirical_full_min 0.822