Organo-cation catalyzed enantioselective α-hydroxylation of pyridinone-fused lactones: asymmetric synthesis of SN-38 and irinotecan.
Tian, Jin-Rui; Qiao, Yu-Hao; Zhuang, Qing-Bo; Fan, Rong; Li, Zhen; Zhang, Xiao-Ming; Zhang, Fu-Min; Tu, Yong-Qiang; Chemical communications (Cambridge, England) 60 (2024) 9954–9957; doi:10.1039/d4cc03580a

data_7133482
_publ_section_title
;
 Organo-cation catalyzed enantioselective &#x3b1;-hydroxylation of
 pyridinone-fused lactones: asymmetric synthesis of SN-38 and irinotecan.
;
_journal_issue                   73
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9954
_journal_page_last               9957
_journal_paper_doi               10.1039/d4cc03580a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H15 N O4'
_chemical_formula_sum            'C13 H15 N O4'
_chemical_formula_weight         249.26
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-14 deposited with the CCDC.	2024-08-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.518(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.5054(2)
_cell_length_b                   10.0086(2)
_cell_length_c                   8.5104(2)
_cell_measurement_reflns_used    6934
_cell_measurement_temperature    302.44(10)
_cell_measurement_theta_max      75.8580
_cell_measurement_theta_min      4.4370
_cell_volume                     598.73(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (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      air
_diffrn_ambient_temperature      302.44(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.964
_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     57.00 100.00   0.50    0.05    --  104.27 -94.00   0.00   86
  2  \w     36.00  93.00   0.50    0.05    --  104.27 -94.00 -30.00  114
  3  \w     35.00  73.00   0.50    0.05    --  104.27 -94.00 -60.00   76
  4  \w     78.00 104.00   0.50    0.05    --  104.27 -94.00-120.00   52
  5  \w     34.00  59.00   0.50    0.05    --  104.27 -94.00-120.00   50
  6  \w    -25.00   0.00   0.50    0.05    --   46.54 -13.00  97.00   50
  7  \w   -121.00 -60.00   0.50    0.05    --  -46.54 -13.00  97.00  122
  8  \w   -111.00 -79.00   0.50    0.05    -- -102.00 -77.00 -30.00   64
  9  \w   -163.00-138.00   0.50    0.05    -- -102.00 -77.00  90.00   50
 10  \w   -173.00-127.00   0.50    0.05    -- -102.00 -77.00 120.00   92
 11  \w   -160.00-135.00   0.50    0.05    -- -102.00 -77.00 -30.00   50
 12  \w   -104.00 -79.00   0.50    0.05    -- -102.00 -77.00   0.00   50
 13  \w   -107.00 -79.00   0.50    0.05    -- -102.00 -77.00  30.00   56
 14  \w   -118.00 -82.00   0.50    0.05    -- -102.00 -71.00  48.88   72
 15  \w   -105.00 -79.00   0.50    0.05    -- -102.00 -76.00  64.45   52
 16  \w   -105.00 -80.00   0.50    0.05    -- -102.00 -77.00  90.00   50
 17  \w   -154.00-123.00   0.50    0.05    -- -102.00 -68.00 -57.45   62
 18  \w   -109.00 -84.00   0.50    0.05    -- -102.00 -64.00 -31.78   50
 19  \w   -115.00 -84.00   0.50    0.05    -- -102.00 -68.00 -57.45   62
 20  \w   -168.00 -86.00   0.50    0.05    -- -102.00 -64.00  30.30  164
 21  \w   -120.00 -86.00   0.50    0.05    -- -102.00 -61.00   0.00   68
 22  \w   -112.00 -87.00   0.50    0.05    -- -102.00 -61.00 -30.00   50
 23  \w   -111.00 -86.00   0.50    0.05    -- -102.00 -60.00  -5.81   50
 24  \w   -166.00-140.00   0.50    0.05    -- -102.00 -60.00  -5.81   52
 25  \w   -126.00 -86.00   0.50    0.05    -- -102.00 -59.00 -16.35   80
 26  \w   -110.00 -85.00   0.50    0.05    -- -102.00 -61.00  60.00   50
 27  \w   -170.00-124.00   0.50    0.05    -- -102.00 -47.00  40.11   92
 28  \w   -172.00-146.00   0.50    0.05    -- -102.00 -59.00 -16.35   52
 29  \w   -118.00 -93.00   0.50    0.05    -- -102.00 -47.00  40.11   50
 30  \w   -133.00-108.00   0.50    0.05    -- -102.00 -13.00  97.00   50
 31  \w   -139.00 -90.00   0.50    0.05    -- -102.00 -45.00  60.00   98
 32  \w    -81.00 -34.00   0.50    0.05    --  -46.54 -19.00   0.00   94
 33  \w   -121.00 -91.00   0.50    0.05    -- -102.00 -30.00 -60.00   60
 34  \w    -87.00 -14.00   0.50    0.05    --  -46.54 125.00  60.00  146
 35  \w    -64.00 -29.00   0.50    0.05    -- -102.00  61.00  60.00   70
 36  \w    -68.00 -29.00   0.50    0.05    -- -102.00  61.00  90.00   78
 37  \w    -69.00 -32.00   0.50    0.05    -- -102.00  61.00  30.00   74
 38  \w    -67.00 -30.00   0.50    0.05    -- -102.00  61.00-180.00   74
 39  \w    -21.00   4.00   0.50    0.05    --  -46.54  13.00 -90.00   50
 40  \w      2.00  27.00   0.50    0.05    --  -46.54  19.00 -30.00   50
 41  \w     88.00 119.00   0.50    0.05    --   46.54  77.00  30.00   62
 42  \w     74.00 100.00   0.50    0.05    --   46.54  77.00   0.00   52
 43  \w     25.00  81.00   0.50    0.05    --   46.54  77.00  30.00  112
 44  \w     26.00  64.00   0.50    0.05    --   46.54  77.00   0.00   76
 45  \w     25.00  58.00   0.50    0.05    --   46.54  77.00 -60.00   66
 46  \w     36.00  76.00   0.50    0.05    --   46.54  37.00   0.00   80
 47  \w     34.00  59.00   0.50    0.05    --   46.54  57.00 -30.00   50
 48  \w     43.00  79.00   0.50    0.05    --   46.54  13.00 -90.00   72
 49  \w     86.00 117.00   0.50    0.05    --  104.27  77.00 -90.00   62
 50  \w     85.00 111.00   0.50    0.05    --  104.27  77.00 -30.00   52
 51  \w     82.00 108.00   0.50    0.05    --  104.27  77.00   0.00   52
 52  \w    149.00 174.00   0.50    0.05    --  104.27  77.00 -30.00   50
 53  \w     88.00 166.00   0.50    0.05    --  104.27  61.00 -90.00  156
 54  \w     99.00 134.00   0.50    0.05    --  104.27  13.00 -90.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.2154637000
_diffrn_orient_matrix_UB_12      0.0279377000
_diffrn_orient_matrix_UB_13      -0.0622318000
_diffrn_orient_matrix_UB_21      0.0064282000
_diffrn_orient_matrix_UB_22      0.0039050000
_diffrn_orient_matrix_UB_23      0.1829133000
_diffrn_orient_matrix_UB_31      0.0395833000
_diffrn_orient_matrix_UB_32      0.1512781000
_diffrn_orient_matrix_UB_33      0.0065911000
_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  0.0256
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            7782
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.996
_diffrn_reflns_theta_min         5.550
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.858
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       block
_exptl_crystal_F_000             264
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.194
_refine_diff_density_min         -0.145
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 927 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2258
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0518P)^2^+0.0442P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0822
_refine_ls_wR_factor_ref         0.0832
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.894
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                2200
_reflns_number_total             2258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03580a2.cif
_cod_data_source_block           tianjinrui-tyq_1113_auto
_cod_depositor_comments          'Adding full bibliography for 7133482.cif.'
_cod_database_code               7133482
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,H11B)
1.b Aromatic/amide H refined with riding coordinates:
 C1(H1A)
1.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C)
1.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              95310
_shelx_hkl_checksum              9146
_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 1.435
_oxdiff_exptl_absorpt_empirical_full_min 0.617