Discovery and heterologous biosynthesis of glycosylated polyketide luteodienoside A reveals unprecedented glucinol-mediated product offloading by a fungal carnitine <i>O</i>-acyltransferase domain.
Arishi, Amr A.; Shang, Zhuo; Lacey, Ernest; Crombie, Andrew; Vuong, Daniel; Li, Hang; Bracegirdle, Joe; Turner, Peter; Lewis, William; Flematti, Gavin R.; Piggott, Andrew M.; Chooi, Yit-Heng; Chemical science 15 (2024) 3349–3356; doi:10.1039/d3sc05008d

data_1570832
_publ_section_title
;
 Discovery and heterologous biosynthesis of glycosylated polyketide
 luteodienoside A reveals unprecedented glucinol-mediated product
 offloading by a fungal carnitine <i>O</i>-acyltransferase domain.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              3349
_journal_page_last               3356
_journal_paper_doi               10.1039/d3sc05008d
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H38 O13, 4(H2 O)'
_chemical_formula_sum            'C23 H46 O17'
_chemical_formula_weight         594.60
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-09-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-14 deposited with the CCDC.	2024-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.60006(18)
_cell_length_b                   7.7434(3)
_cell_length_c                   55.3300(13)
_cell_measurement_reflns_used    15913
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.9430
_cell_measurement_theta_min      4.7660
_cell_volume                     2827.75(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5861
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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   -116.00  -9.00   1.00   10.00    --  -39.26 -57.00  30.00  107
  2  \w    -31.00  -3.00   1.00   10.00    --  -39.26  44.00-125.00   28
  3  \w     15.00  56.00   1.00   10.00    --   39.26  57.00  30.00   41
  4  \w    -31.00  -5.00   1.00   10.00    --   39.26 -57.00-120.00   26
  5  \w     54.00  80.00   1.00   40.00    --  116.00 -61.00-150.00   26
  6  \w     44.00  88.00   1.00   40.00    --  116.00 -61.00 -60.00   44
  7  \w    117.00 151.00   1.00   40.00    --  116.00 -66.00 133.99   34
  8  \w     50.00  75.00   1.00   40.00    --  116.00 -45.00-120.00   25
  9  \w    126.00 168.00   1.00   40.00    --  116.00  44.00-125.00   42
 10  \w    105.00 147.00   1.00   40.00    --  116.00 -45.00-120.00   42
 11  \w    128.00 160.00   1.00   40.00    --  116.00  45.00   0.00   32
 12  \w     84.00 178.00   1.00   40.00    --  116.00  61.00-150.00   94
 13  \w    101.00 126.00   1.00   40.00    --  116.00 -61.00-150.00   25
 14  \w     86.00 112.00   1.00   40.00    --  116.00  45.00   0.00   26
 15  \w     89.00 128.00   1.00   40.00    --  116.00  45.00 150.00   39
 16  \w    116.00 148.00   1.00   40.00    --  116.00  61.00 -90.00   32
 17  \w     73.00 100.00   1.00   40.00    --  116.00 -66.00 133.99   27
 18  \w     98.00 123.00   1.00   40.00    --  116.00  45.00 -90.00   25
 19  \w    111.00 168.00   1.00   40.00    --  116.00  32.00 -15.53   57
 20  \w     46.00  71.00   1.00   10.00    --   39.26 -38.00-150.00   25
 21  \w      7.00  32.00   1.00   10.00    --   39.26 -38.00-150.00   25
 22  \w     68.00  94.00   1.00   10.00    --   39.26  57.00   0.00   26
 23  \w     38.00  64.00   1.00   40.00    --  116.00 -37.00-165.71   26
 24  \w    109.00 134.00   1.00   40.00    --  116.00  45.00  30.00   25
 25  \w     85.00 131.00   1.00   40.00    --  116.00  45.00 120.00   46
 26  \w     94.00 120.00   1.00   40.00    --  116.00 -69.00 -63.27   26
 27  \w    102.00 128.00   1.00   40.00    --  116.00  45.00  60.00   26
 28  \w     88.00 142.00   1.00   40.00    --  116.00  61.00 150.00   54
 29  \w     50.00  75.00   1.00   40.00    --  116.00 -61.00  90.00   25
 30  \w     91.00 116.00   1.00   40.00    --  116.00  45.00 -60.00   25
 31  \w     88.00 113.00   1.00   40.00    --  116.00  61.00 -60.00   25
 32  \w     54.00  80.00   1.00   40.00    --  116.00 -61.00 120.00   26
 33  \w    107.00 133.00   1.00   40.00    --  116.00 -61.00 120.00   26
 34  \w    122.00 148.00   1.00   40.00    --  116.00  45.00-150.00   26
 35  \w    103.00 147.00   1.00   40.00    --  116.00 -37.00-165.71   44
 36  \w    105.00 150.00   1.00   40.00    --  116.00 -34.00-134.27   45
 37  \w    120.00 145.00   1.00   40.00    --  116.00  45.00 150.00   25
 38  \w     81.00 106.00   1.00   40.00    --  116.00 -61.00  30.00   25
 39  \w     39.00  65.00   1.00   40.00    --  116.00 -34.00-134.27   26
 40  \w    -42.00 -11.00   1.00   10.00    --  -39.26 -57.00-180.00   31
 41  \w     33.00  67.00   1.00   10.00    --   39.26 -68.00 -84.30   34
 42  \w     49.00  74.00   1.00   10.00    --   39.26 -70.00  -4.07   25
 43  \w     44.00  70.00   1.00   10.00    --   39.26 -69.00  34.56   26
 44  \w    -40.00 -14.00   1.00   10.00    --   39.26 -70.00  -4.07   26
 45  \w     49.00  74.00   1.00   10.00    --   39.26 -68.00 -49.39   25
 46  \w    -32.00  10.00   1.00   10.00    --   39.26 -68.00 -84.30   42
 47  \w     35.00  74.00   1.00   10.00    --   39.26 -69.00-145.73   39
 48  \w     18.00  44.00   1.00   10.00    --   39.26  57.00-150.00   26
 49  \w    -33.00  65.00   1.00   10.00    --   39.26 -57.00 120.00   98
 50  \w     51.00 110.00   1.00   40.00    --  116.00 -70.00-153.63   59
 51  \w     64.00 120.00   1.00   40.00    --  116.00 -70.00 -37.18   56
 52  \w     85.00 111.00   1.00   40.00    --  116.00 -68.00   4.44   26
 53  \w     48.00  94.00   1.00   40.00    --  116.00 -49.00  29.34   46
 54  \w    128.00 153.00   1.00   40.00    --  116.00  45.00 -60.00   25
 55  \w     81.00 107.00   1.00   40.00    --  116.00 -70.00-109.34   26
 56  \w     45.00 113.00   1.00   40.00    --  116.00 -70.00  65.29   68
 57  \w     59.00 106.00   1.00   40.00    --  116.00 -70.00 -74.79   47
 58  \w     69.00  95.00   1.00   40.00    --  116.00 -50.00 -33.70   26
 59  \w     69.00  95.00   1.00   40.00    --  116.00 -53.00 -90.68   26
 60  \w     84.00 136.00   1.00   40.00    --  116.00 -69.00 152.99   52
 61  \w     56.00 101.00   1.00   40.00    --  116.00 -66.00 134.94   45
 62  \w    124.00 149.00   1.00   40.00    --  116.00 -33.00 127.55   25
 63  \w     72.00 107.00   1.00   40.00    --  116.00 -70.00 -10.96   35
 64  \w     95.00 156.00   1.00   40.00    --  116.00  61.00-180.00   61
 65  \w     97.00 123.00   1.00   40.00    --  116.00  45.00   0.00   26
 66  \w     85.00 111.00   1.00   40.00    --  116.00  45.00 -90.00   26
 67  \w    117.00 143.00   1.00   40.00    --  116.00  45.00 -90.00   26
 68  \w    125.00 151.00   1.00   40.00    --  116.00  45.00  30.00   26
 69  \w    130.00 156.00   1.00   40.00    --  116.00  61.00  60.00   26
 70  \w     75.00 101.00   1.00   40.00    --  116.00 -33.00 127.55   26
 71  \w    102.00 128.00   1.00   40.00    --  116.00  45.00-180.00   26
 72  \w    128.00 170.00   1.00   40.00    --  116.00  61.00 120.00   42
 73  \w    151.00 176.00   1.00   40.00    --  116.00  45.00   0.00   25
 74  \w     48.00  73.00   1.00   40.00    --  116.00 -33.00 127.55   25
 75  \w    119.00 145.00   1.00   40.00    --  116.00  45.00 -30.00   26
 76  \w     41.00  95.00   1.00   40.00    --  116.00 -45.00 -30.00   54
 77  \w     58.00  84.00   1.00   40.00    --  116.00 -45.00  90.00   26
 78  \w     38.00 110.00   1.00   40.00    --  116.00 -70.00 117.72   72
 79  \w    -76.00 -50.00   1.00   10.00    --  -39.26 -57.00-120.00   26
 80  \w   -116.00 -84.00   1.00   10.00    --  -39.26 -57.00-120.00   32
 81  \w    -40.00  -7.00   1.00   10.00    --  -39.26 -57.00-120.00   33
 82  \w      9.00  41.00   1.00   10.00    --   44.00  70.00 -15.71   32
 83  \w     96.00 122.00   1.00   10.00    --   44.00  70.00 -15.71   26
 84  \w     15.00  59.00   1.00   10.00    --   48.00  70.00 119.08   44
 85  \w     16.00  42.00   1.00   10.00    --   48.00  70.00  70.24   26
 86  \w    104.00 129.00   1.00   10.00    --   48.00  70.00  70.24   25
 87  \w     44.00  70.00   1.00   10.00    --   48.00  70.00  70.24   26
 88  \w     18.00  51.00   1.00   10.00    --   52.00  70.00 -78.47   33
 89  \w     27.00  53.00   1.00   10.00    --   56.00  70.00 -50.12   26
 90  \w     21.00  48.00   1.00   10.00    --   56.00  70.00 177.42   27
 91  \w    111.00 137.00   1.00   10.00    --   60.00  69.00 141.02   26
 92  \w     25.00  53.00   1.00   10.00    --   60.00  69.00 141.02   28
 93  \w     26.00  52.00   1.00   10.00    --   60.00  70.00   5.68   26
 94  \w    120.00 145.00   1.00   10.00    --   64.00  69.00-126.99   25
 95  \w     29.00  56.00   1.00   10.00    --   64.00  70.00  80.14   27
 96  \w     30.00  56.00   1.00   10.00    --   64.00  69.00-126.99   26
 97  \w     33.00  66.00   1.00   10.00    --   68.00  69.00 162.43   33
 98  \w     33.00  58.00   1.00   10.00    --   68.00  66.00-152.12   25
 99  \w    123.00 148.00   1.00   10.00    --   68.00  66.00-152.12   25
100  \w    123.00 149.00   1.00   10.00    --   68.00  69.00 162.43   26
101  \w     65.00 100.00   1.00   10.00    --   72.00 -70.00 130.05   35
102  \w     24.00  50.00   1.00   10.00    --   72.00 -70.00 130.05   26
103  \w     42.00  68.00   1.00   10.00    --   76.00  68.00  17.13   26
104  \w     53.00  88.00   1.00   40.00    --   80.00  68.00 -16.25   35
105  \w     44.00  69.00   1.00   40.00    --   80.00  65.00 126.47   25
106  \w     45.00  72.00   1.00   40.00    --   80.00  70.00-126.60   27
107  \w     51.00 104.00   1.00   40.00    --   84.00  68.00 -92.60   53
108  \w     51.00  84.00   1.00   40.00    --   84.00  60.00-159.81   33
109  \w     49.00  55.00   1.00   40.00    --   84.00  69.00 -51.94    6
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1215754000
_diffrn_orient_matrix_UB_12      0.0102130000
_diffrn_orient_matrix_UB_13      0.0237012000
_diffrn_orient_matrix_UB_21      -0.0479216000
_diffrn_orient_matrix_UB_22      -0.1912823000
_diffrn_orient_matrix_UB_23      0.0053099000
_diffrn_orient_matrix_UB_31      0.1931994000
_diffrn_orient_matrix_UB_32      -0.0540344000
_diffrn_orient_matrix_UB_33      -0.0136102000
_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  0.0667
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       69
_diffrn_reflns_limit_l_min       -69
_diffrn_reflns_number            53625
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.992
_diffrn_reflns_theta_min         4.795
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.028
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.686
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       needle
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 2109 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         5946
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0562
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0001P)^2^+4.7117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0992
_refine_ls_wR_factor_ref         0.1013
_reflns_Friedel_coverage         0.705
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                5556
_reflns_number_total             5946
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05008d2.cif
_cod_data_source_block           amp17pt2_s1582_2
_cod_depositor_comments          'Adding full bibliography for 1570832.cif.'
_cod_original_cell_volume        2827.75(16)
_cod_database_code               1570832
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         C23H46O17
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.788
_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, All O(H,H) groups
2. Restrained distances
 O2W-H2WB \\sim O2W-H2WA \\sim O1W-H1WA \\sim O1W-H1WB \\sim O3W-H3WB \\sim
O3W-H3WA \\sim O4W-H4WA ~
 O4W-H4WB
 with sigma of 0.02
 H4WB-H4WA \\sim H3WA-H3WB \\sim H2WA-H2WB \\sim H1WA-H1WB
 with sigma of 0.02
 O3'-H3'A \\sim O4"-H4"A \\sim O5"-H5"A \\sim O1"-H1"A \\sim O2"-H2" \\sim
O3"-H3" \\sim O1'-H1' \\sim O2'-
 H2' \\sim O3-H3A
 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3), C1"(H1"), C2"(H2"A), C3"(H3"A), C4"(H4"), C5"(H5"), C6"(H6"),
 C1'(H1'A), C2'(H2'A), C3'(H3'), C4'(H4'), C5'(H5')
3.b Secondary CH2 refined with riding coordinates:
 C6'(H6'A,H6'B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7)
3.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_res_checksum              66636
_shelx_hkl_checksum              39734
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.721