Total synthesis, biological evaluation and biosynthetic re-evaluation of <i>Illicium</i>-derived neolignans.
Arnold, Robert E.; Saska, Jan; Mesquita-Ribeiro, Raquel; Dajas-Bailador, Federico; Taylor, Laurence; Lewis, William; Argent, Stephen; Shao, Huiling; Houk, Kendall N.; Denton, Ross M.; Chemical science 15 (2024) 11783–11793; doi:10.1039/d4sc03232b

data_1571943
_publ_section_title
;
 Total synthesis, biological evaluation and biosynthetic re-evaluation of
 <i>Illicium</i>-derived neolignans.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              11783
_journal_page_last               11793
_journal_paper_doi               10.1039/d4sc03232b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C27 H26 O3'
_chemical_formula_sum            'C27 H26 O3'
_chemical_formula_weight         398.48
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-01-23 deposited with the CCDC.	2024-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.545(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.5253(3)
_cell_length_b                   11.2640(3)
_cell_length_c                   33.0222(10)
_cell_measurement_reflns_used    11417
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.4190
_cell_measurement_theta_min      2.6550
_cell_volume                     4282.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      'N2 gas'
_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 0.976
_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   -119.00 -14.00   1.00   30.00    --  -42.81 -19.00  30.00  105
  2  \w    -50.00  28.00   1.00   30.00    --  -42.81  38.00-150.00   78
  3  \w     23.00  96.00   1.00   30.00    --   42.81-125.00-120.00   73
  4  \w     34.00  98.00   1.00  120.00    --  103.00 -45.00   0.00   64
  5  \w     94.00 175.00   1.00  120.00    --  103.00 125.00-120.00   81
  6  \w     22.00 110.00   1.00  120.00    --  103.00 -94.00 -30.00   88
  7  \w     94.00 175.00   1.00  120.00    --  103.00 125.00-180.00   81
  8  \w     67.00 178.00   1.00  120.00    --  103.00  15.00 -30.00  111
  9  \w     34.00  98.00   1.00  120.00    --  103.00 -45.00  90.00   64
 10  \w     73.00 175.00   1.00  120.00    --  103.00  77.00 150.00  102
 11  \w     34.00  98.00   1.00  120.00    --  103.00 -45.00 -90.00   64
 12  \w    -50.00  28.00   1.00   30.00    --  -42.81  38.00   0.00   78
 13  \w     19.00 112.00   1.00   30.00    --   42.81  57.00 -30.00   93
 14  \w     12.00 115.00   1.00   30.00    --   42.81  77.00-150.00  103
 15  \w     30.00  64.00   1.00  120.00    --  103.00 -30.00-180.00   34
;
_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      -0.0103967000
_diffrn_orient_matrix_UB_12      0.0361423000
_diffrn_orient_matrix_UB_13      0.0446910000
_diffrn_orient_matrix_UB_21      0.0691336000
_diffrn_orient_matrix_UB_22      -0.1113632000
_diffrn_orient_matrix_UB_23      0.0134511000
_diffrn_orient_matrix_UB_31      0.1140700000
_diffrn_orient_matrix_UB_32      0.0706979000
_diffrn_orient_matrix_UB_33      -0.0016557000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            32607
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.971
_diffrn_reflns_theta_min         2.679
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.657
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.236
_exptl_crystal_description       plate
_exptl_crystal_F_000             1696
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethylacetate, pentane'
_exptl_crystal_size_max          0.418
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.351
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     556
_refine_ls_number_reflns         8478
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0916
_refine_ls_R_factor_gt           0.0707
_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^)+(0.0437P)^2^+6.0770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1523
_refine_ls_wR_factor_ref         0.1651
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6588
_reflns_number_total             8478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03232b2.cif
_cod_data_source_block           2-simonsol-C
_cod_depositor_comments
'Adding full bibliography for 1571943--1571950.cif.'
_cod_database_code               1571943
_nottingham_internal_coll_name   REARDK
_nottingham_internal_coll_number 17991
_nottingham_internal_coll_client REA/RD
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '30.00, 120.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczlt
_nottingham_internal_coll_date   30/11/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 03/12/2018
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 03/12/2018
_nottingham_internal_solution_user pczlt
_nottingham_internal_refinement_date 09/08/2022
_nottingham_internal_refinement_user pczlt/pczspa
_nottingham_internal_validation_date 09/08/2022
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 09/08/2022
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C27 H26 O3'
_chemical_oxdiff_usercomment
'REARDK3 #17991 GVA-1541 IN FOMBLIN FILM ON A MICROMOUNT FOR RA/RD'
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.780
_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 O(H) groups
2. Restrained distances
 C20B-C19B \\sim C20A-C19A
 with sigma of 0.02
 C18B-C19B \\sim C19A-C18A
 with sigma of 0.02
 C18B-C15A \\sim C18A-C15A
 with sigma of 0.02
3. Restrained planarity
 C16A, C15A, C18B, C14A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C18B \\sim C18A \\sim C19B \\sim C19A \\sim C20B \\sim C20A \\sim C15A: within
0.01A with sigma of 3.5 and sigma for terminal atoms of 0.005 within 0.01A
5. Rigid body (RIGU) restrains
 C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20C)=Sof(H20D)=Sof(C18B)=Sof(H18C)=
 Sof(H18D)=1-FVAR(1)
 Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=
 Sof(H20B)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C6A(H6A), C6B(H6B)
7.b Secondary CH2 refined with riding coordinates:
 C7A(H7AA,H7AB), C8A(H8AA,H8AB), C18A(H18A,H18B), C28A(H28A,H28B), C7B(H7BA,
 H7BB), C8B(H8BA,H8BB), C3(H3C,H3D), C28B(H28C,H28D), C18B(H18C,H18D)
7.c Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C9A(H9A), C14A(H14A), C16A(H16A), C19A(H19A), C23A(H23A),
 C24A(H24A), C26A(H26A), C29A(H29A), C3B(H3B), C4B(H4B), C9B(H9B), C14B(H14B),
 C16B(H16B), C1(H1), C23B(H23B), C24B(H24B), C26B(H26B), C29B(H29B), C19B(H19B)
7.d X=CH2 refined with riding coordinates:
 C10A(H10A,H10B), C20A(H20A,H20B), C30A(H30A,H30B), C10B(H10C,H10D), C2(H2A,
 H2B), C30B(H30C,H30D), C20B(H20C,H20D)
7.e Idealised tetrahedral OH refined as rotating group:
 O27A(H27A), O27B(H27B)
;
_shelx_res_checksum              88485
_shelx_hkl_checksum              79798
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 2.151
_oxdiff_exptl_absorpt_empirical_full_min 0.648