A bioinspired, one-step total synthesis of peshawaraquinone.
Vieira de Castro, Tomás; Huang, David M.; Sumby, Christopher J.; Lawrence, Andrew L.; George, Jonathan H.; Chemical science 14 (2023) 950–954; doi:10.1039/d2sc05377b

data_1568166
_publ_section_title
;
 A bioinspired, one-step total synthesis of peshawaraquinone.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              950
_journal_page_last               954
_journal_paper_doi               10.1039/d2sc05377b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C30 H24 O6, C3.5 H4'
_chemical_formula_sum            'C33.5 H28 O6'
_chemical_formula_weight         526.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2c4lty
_audit_creation_date             2022-06-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-15 deposited with the CCDC.	2022-12-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.6800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6590(2)
_cell_length_b                   8.38590(10)
_cell_length_c                   17.8047(2)
_cell_measurement_reflns_used    12921
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.3830
_cell_measurement_theta_min      3.4470
_cell_volume                     2633.75(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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.937
_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    -79.00  23.00   0.50    0.74    --  -48.77  95.00  82.00  204
  2  \w     -9.00  79.00   0.50    0.74    --   48.77 -95.00 -27.00  176
  3  \w    -79.00 -18.00   0.50    2.94    --  -90.00  95.00  82.00  122
  4  \w   -161.00 -83.00   0.50    2.94    --  -90.00 -95.00 -27.00  156
  5  \w     35.00 105.00   0.50    2.94    --  106.92 -95.00 -27.00  140
  6  \w    -17.00  26.00   0.50    0.74    --  -48.77  19.00-180.00   86
  7  \w   -121.00 -94.00   0.50    0.74    --  -48.77-125.00 150.00   54
  8  \w    -41.00  23.00   0.50    0.74    --  -48.77  38.00-150.00  128
  9  \w     39.00 123.00   0.50    0.74    --   48.77  19.00 -90.00  168
 10  \w     39.00 121.00   0.50    0.74    --   48.77  38.00  60.00  164
 11  \w   -161.00-106.00   0.50    2.94    --  -90.00 -99.00-150.00  110
 12  \w   -161.00-103.00   0.50    2.94    --  -90.00 -57.00   0.00  116
 13  \w   -161.00-103.00   0.50    2.94    --  -90.00 -57.00-120.00  116
 14  \w    -64.00 -27.00   0.50    2.94    --  -90.00  57.00  30.00   74
 15  \w    -66.00 -25.00   0.50    2.94    --  -90.00  57.00 -90.00   82
 16  \w    -68.00 -26.00   0.50    2.94    --  -90.00  57.00  60.00   84
 17  \w   -153.00-117.00   0.50    2.94    --  -90.00 -57.00  90.00   72
 18  \w     74.00 106.00   0.50    2.94    --  106.92-125.00 120.00   64
 19  \w     35.00  60.00   0.50    2.94    --  106.92 -57.00 120.00   50
 20  \w     38.00  69.00   0.50    2.94    --  106.92-125.00 120.00   62
 21  \w     36.00  65.00   0.50    2.94    --  106.92 -57.00-120.00   58
 22  \w     35.00  61.00   0.50    2.94    --  106.92 -57.00  30.00   52
 23  \w     41.00  66.00   0.50    2.94    --  106.92 -57.00-150.00   50
 24  \w     36.00  64.00   0.50    2.94    --  106.92 -57.00   0.00   56
 25  \w     77.00 102.00   0.50    2.94    --  106.92 -99.00  30.00   50
 26  \w     38.00  66.00   0.50    2.94    --  106.92 -57.00  90.00   56
 27  \w     35.00  61.00   0.50    2.94    --  106.92 -57.00-180.00   52
 28  \w    117.00 159.00   0.50    2.94    --  106.92  95.00  82.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0099405000
_diffrn_orient_matrix_UB_12      -0.1513564000
_diffrn_orient_matrix_UB_13      -0.0476186000
_diffrn_orient_matrix_UB_21      -0.0657857000
_diffrn_orient_matrix_UB_22      -0.0801084000
_diffrn_orient_matrix_UB_23      0.0395333000
_diffrn_orient_matrix_UB_31      -0.0565780000
_diffrn_orient_matrix_UB_32      0.0665591000
_diffrn_orient_matrix_UB_33      -0.0605872000
_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  0.0345
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25450
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.166
_diffrn_reflns_theta_min         3.445
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.737
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71828
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       plank
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.884
_refine_diff_density_min         -0.383
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         5234
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0572
_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^)+(0.0741P)^2^+2.7393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1490
_refine_ls_wR_factor_ref         0.1535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4689
_reflns_number_total             5234
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05377b2.cif
_cod_data_source_block           1jg1r_auto
_cod_depositor_comments          'Adding full bibliography for 1568166.cif.'
_cod_original_formula_sum        'C33.50 H28 O6'
_cod_database_code               1568166
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H24O6
_chemical_oxdiff_usercomment     'from toluene'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Shared sites
{C21A, C21B}
3. Uiso/Uaniso restraints and constraints
C21A \\sim C21B \\sim C22 \\sim C23 \\sim C24B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Uanis(C21A) = Uanis(C21B)
4. Rigid body (RIGU) restrains
 C21A, C21B, C22, C23, C24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C21A(0.5) H21A(0.5) C21B(0.5) C24B(0.5) H24A(0.5) H24B(0.5)
 H24C(0.5)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C11'(H11'), C12(H12)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C5'(H5'), C6(H6), C6'(H6'), C7(H7), C7'(H7'), C8(H8), C8'(H8'),
 C12'(H12'), C22(H22), C23(H23), C21A(H21A)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14'(H14D,H14E,H14F), C15'(H15C,H15D,H15E), C24B(H24A,
 H24B,H24C)
6.e Idealised tetrahedral OH refined as rotating group:
 O4'(H4')
;
_shelx_res_checksum              70953
_shelx_hkl_checksum              83957
_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 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.651