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_7133037
_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                 107.749(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4612(2)
_cell_length_b                   10.51960(10)
_cell_length_c                   20.4828(3)
_cell_measurement_reflns_used    42076
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.7860
_cell_measurement_theta_min      4.5060
_cell_volume                     2557.22(7)
_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 0.999
_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     -5.00  20.00   1.00    4.00    --   30.00  92.00  10.38   25
  2  \w     -7.00  18.00   1.00    4.00    --   30.00  95.00-129.62   25
  3  \w     -7.00  18.00   1.00    4.00    --   30.00  94.00  81.51   25
  4  \w    -43.00  26.00   1.00    4.00    --  -43.06  57.00-150.00   69
  5  \w    -21.00  26.00   1.00    4.00    --  -43.06  38.00 150.00   47
  6  \w     24.00  53.00   1.00    4.00    --   43.06  38.00   0.00   29
  7  \w     27.00  96.00   1.00    4.00    --   43.06-125.00  60.00   69
  8  \w     21.00 114.00   1.00    4.00    --   43.06  38.00-180.00   93
  9  \w     14.00  39.00   1.00    4.00    --   46.00  82.00-147.15   25
 10  \w     14.00  42.00   1.00    4.00    --   46.00  81.00 -76.08   28
 11  \w     15.00  40.00   1.00    4.00    --   46.00  80.00 169.89   25
 12  \w     15.00  42.00   1.00    4.00    --   46.00  78.00  29.04   27
 13  \w     14.00  39.00   1.00    4.00    --   46.00  81.00 107.00   25
 14  \w     27.00  77.00   1.00    4.00    --   54.00  70.00  39.95   50
 15  \w     78.00 123.00   1.00    4.00    --   54.00  70.00  39.95   45
 16  \w     32.00  69.00   1.00    4.00    --   58.00  71.00-162.24   37
 17  \w     31.00  56.00   1.00    4.00    --   58.00  69.00 131.30   25
 18  \w     78.00 128.00   1.00    4.00    --   58.00  71.00-162.24   50
 19  \w     35.00  66.00   1.00    4.00    --   62.00  70.00 171.73   31
 20  \w     34.00  60.00   1.00    4.00    --   62.00  71.00 -29.91   26
 21  \w     40.00  67.00   1.00    4.00    --   66.00  64.00 113.40   27
 22  \w     39.00  87.00   1.00    4.00    --   66.00  69.00 -13.02   48
 23  \w     38.00  64.00   1.00    4.00    --   66.00  71.00  16.03   26
 24  \w     38.00  64.00   1.00    4.00    --   66.00  69.00 -65.39   26
 25  \w     44.00  71.00   1.00    4.00    --   70.00  63.00  86.40   27
 26  \w    101.00 127.00   1.00    4.00    --   70.00  69.00-118.12   26
 27  \w     42.00  77.00   1.00    4.00    --   70.00  69.00-118.12   35
 28  \w     42.00  69.00   1.00    4.00    --   70.00  70.00-145.64   27
 29  \w     47.00  73.00   1.00   16.00    --   74.00  66.00 139.87   26
 30  \w     47.00  77.00   1.00   16.00    --   74.00  69.00 -70.99   30
 31  \w    118.00 144.00   1.00   16.00    --   74.00  71.00  43.29   26
 32  \w     46.00  76.00   1.00   16.00    --   74.00  71.00  43.29   30
 33  \w    110.00 136.00   1.00   16.00    --   74.00  66.00 139.87   26
 34  \w     50.00  81.00   1.00   16.00    --   78.00  70.00 158.80   31
 35  \w     60.00  85.00   1.00   16.00    --   86.00  68.00 -58.27   25
 36  \w    100.00 160.00   1.00   16.00    --   94.00  70.00  37.03   60
 37  \w     66.00  93.00   1.00   16.00    --   94.00  70.00  37.03   27
 38  \w     44.00 113.00   1.00   16.00    --  100.81-125.00-120.00   69
 39  \w     77.00 104.00   1.00   16.00    --  100.81  56.00 172.56   27
 40  \w    110.00 162.00   1.00   16.00    --  100.81  61.00 -60.00   52
 41  \w     77.00 104.00   1.00   16.00    --  100.81  61.00 -60.00   27
 42  \w     31.00  92.00   1.00   16.00    --  100.81 -61.00-150.00   61
 43  \w     31.00  80.00   1.00   16.00    --  100.81 -61.00 120.00   49
 44  \w     31.00  56.00   1.00   16.00    --  100.81 -30.00-120.00   25
 45  \w     29.00 113.00   1.00   16.00    --  100.81-125.00   0.00   84
 46  \w     76.00 164.00   1.00   16.00    --  100.81  61.00 -90.00   88
 47  \w     76.00 135.00   1.00   16.00    --  100.81  61.00 120.00   59
 48  \w    119.00 163.00   1.00   16.00    --  100.81  61.00   0.00   44
 49  \w     77.00 166.00   1.00   16.00    --  100.81  59.00 140.97   89
 50  \w     32.00  91.00   1.00   16.00    --  100.81 -61.00 -30.00   59
 51  \w     76.00 103.00   1.00   16.00    --  100.81  61.00   0.00   27
 52  \w    145.00 170.00   1.00   16.00    --  100.81  55.00  24.57   25
 53  \w    118.00 159.00   1.00   16.00    --  100.81  61.00 -30.00   41
 54  \w     77.00 104.00   1.00   16.00    --  100.81  61.00 -30.00   27
 55  \w     77.00 108.00   1.00   16.00    --  100.81  55.00  24.57   31
 56  \w     77.00 117.00   1.00   16.00    --  100.81  61.00-150.00   40
 57  \w     30.00 106.00   1.00   16.00    --  100.81-125.00 150.00   76
 58  \w     76.00 156.00   1.00   16.00    --  100.81  59.00  68.68   80
 59  \w    126.00 170.00   1.00   16.00    --  100.81  63.00-165.42   44
 60  \w     75.00 102.00   1.00   16.00    --  100.81  63.00-165.42   27
 61  \w     76.00 133.00   1.00   16.00    --  100.81  61.00-120.00   57
 62  \w     29.00 113.00   1.00   16.00    --  100.81-125.00 120.00   84
 63  \w     76.00 102.00   1.00   16.00    --  100.81  61.00  90.00   26
 64  \w    121.00 166.00   1.00   16.00    --  100.81  56.00 172.56   45
;
_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      -0.0937789000
_diffrn_orient_matrix_UB_12      -0.0106454000
_diffrn_orient_matrix_UB_13      0.0343632000
_diffrn_orient_matrix_UB_21      0.0302912000
_diffrn_orient_matrix_UB_22      0.1333233000
_diffrn_orient_matrix_UB_23      0.0312964000
_diffrn_orient_matrix_UB_31      -0.0844458000
_diffrn_orient_matrix_UB_32      0.0596577000
_diffrn_orient_matrix_UB_33      -0.0638566000
_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  0.0239
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            47567
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.720
_diffrn_reflns_theta_min         3.723
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.745
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.758
_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    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: EtOAc and pentane'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 4434 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         9978
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0255
_refine_ls_R_factor_gt           0.0247
_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^)+(0.0371P)^2^+0.5226P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0643
_refine_ls_wR_factor_ref         0.0649
_reflns_Friedel_coverage         0.871
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                9719
_reflns_number_total             9978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01788a2.cif
_cod_data_source_block           jmhwlb
_cod_depositor_comments
'Adding full bibliography for 7133037--7133039.cif.'
_cod_database_code               7133037
_nottingham_internal_coll_name   JMHWLB
_nottingham_internal_coll_number 19421
_nottingham_internal_coll_client JM/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '16.00, 4.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczkj1
_nottingham_internal_coll_date   05/04/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 06/04/2023
_nottingham_internal_process_user pczkj1
_nottingham_internal_solution_date 06/04/2023
_nottingham_internal_solution_user pczkj1
_nottingham_internal_refinement_date 23/04/2023
_nottingham_internal_refinement_user pczkj1
_nottingham_internal_self_validation_date 23/04/2023
_nottingham_internal_self_validation_user pczkj1
_nottingham_internal_validation_date pczspa
_nottingham_internal_validation_user 26/04/2023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H28 F3 N O8 S'
_chemical_oxdiff_usercomment
'JMHWLB #19421 GVA-2051 KJ/HWL fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.650
_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
 O1B-H1B = O1A-H1A
 0.84 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C1A(H1AA), C1B(H1BA)
3.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C3A(H3AA,H3AB), C7A(H7AA,H7AB), C8A(H8AA,H8AB), C15A(H15A,
 H15B), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB),
 C15B(H15C,H15D)
3.c Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C18A(H18A), C20A(H20A), C21A(H21A), C5B(H5B), C18B(H18B),
 C20B(H20B), C21B(H21B)
3.d Idealised Me refined as rotating group:
 C12A(H12A,H12B,H12C), C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C22A(H22A,
 H22B,H22C), C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F),
 C22B(H22D,H22E,H22F)
;
_shelx_res_checksum              94925
_olex2_submission_original_sample_id JMHWLB
_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 1.366
_oxdiff_exptl_absorpt_empirical_full_min 0.812