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_1571948
_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         'C19 H19 Br O3'
_chemical_formula_sum            'C19 H19 Br O3'
_chemical_formula_weight         375.25
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-02-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2024-01-23 deposited with the CCDC.	2024-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                66.361(5)
_cell_angle_beta                 82.591(4)
_cell_angle_gamma                75.387(4)
_cell_formula_units_Z            4
_cell_length_a                   11.1367(5)
_cell_length_b                   12.0896(6)
_cell_length_c                   14.1443(7)
_cell_measurement_reflns_used    9461
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.0210
_cell_measurement_theta_min      3.4000
_cell_volume                     1687.31(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.969
_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    -27.00  67.00   1.00    1.00    --   42.81 -57.00  90.00   94
  2  \w     38.00  65.00   1.00    3.00    --  103.32-125.00 150.00   27
  3  \w     38.00  64.00   1.00    3.00    --  103.32-125.00 120.00   26
  4  \w     96.00 121.00   1.00    3.00    --  103.32-125.00 120.00   25
  5  \w     61.00 124.00   1.00    3.00    --  103.32 -77.00   0.00   63
  6  \w     92.00 120.00   1.00    3.00    --  103.32-125.00 -90.00   28
  7  \w     70.00 108.00   1.00    3.00    --  103.32 -94.00 -60.00   38
  8  \w     47.00  87.00   1.00    3.00    --  103.32 -94.00 -90.00   40
  9  \w     39.00  98.00   1.00    3.00    --  103.32 -45.00-120.00   59
 10  \w     34.00  77.00   1.00    3.00    --  103.32 -30.00 -60.00   43
 11  \w     34.00  83.00   1.00    3.00    --  103.32 -30.00-180.00   49
 12  \w     20.00 112.00   1.00    1.00    --   42.81  57.00-120.00   92
 13  \w     76.00 168.00   1.00    3.00    --  103.32  77.00-180.00   92
 14  \w     78.00 124.00   1.00    3.00    --  103.32 125.00 -90.00   46
 15  \w     91.00 171.00   1.00    3.00    --  103.32  30.00  90.00   80
 16  \w    135.00 160.00   1.00    3.00    --  103.32 125.00 120.00   25
 17  \w     84.00 117.00   1.00    3.00    --  103.32 125.00 120.00   33
 18  \w     38.00  74.00   1.00    3.00    --  103.32 -30.00  90.00   36
 19  \w     32.00 133.00   1.00    3.00    --  103.32 -77.00 120.00  101
 20  \w    -17.00  70.00   1.00    1.00    --   42.81 -77.00 -30.00   87
;
_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      -0.0749829000
_diffrn_orient_matrix_UB_12      -0.1019315000
_diffrn_orient_matrix_UB_13      0.0438369000
_diffrn_orient_matrix_UB_21      -0.0419095000
_diffrn_orient_matrix_UB_22      0.0361342000
_diffrn_orient_matrix_UB_23      0.0938547000
_diffrn_orient_matrix_UB_31      -0.1143579000
_diffrn_orient_matrix_UB_32      0.0929788000
_diffrn_orient_matrix_UB_33      -0.0584743000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0214
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12597
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.677
_diffrn_reflns_theta_min         3.413
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.421
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.437
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.477
_exptl_crystal_description       block
_exptl_crystal_F_000             768
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether, petroleum ether'
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.254
_exptl_crystal_size_min          0.105
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         6604
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0406P)^2^+3.5368P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6212
_reflns_number_total             6604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03232b2.cif
_cod_data_source_block           42b
_cod_depositor_comments
'Adding full bibliography for 1571943--1571950.cif.'
_cod_original_cell_volume        1687.30(16)
_cod_database_code               1571948
_nottingham_internal_coll_name   REARDF
_nottingham_internal_coll_number 17454
_nottingham_internal_coll_client REA/RD
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '1.00, 3.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   18/01/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 23/01/2018
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 23/1/2018
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 12/2/2018
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 12/2/2018
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 12/2/2018
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C19 H19 Br O3'
_chemical_oxdiff_usercomment
'REARDF #17454 GVA-1359 IN FOMBLIN FILM ON A MICROMOUNT FOR REA/RD'
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.385
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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
2. Others
 Sof(C49)=Sof(H49C)=Sof(H49D)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51C)=Sof(H51D)=1-
 FVAR(1)
 Sof(C49A)=Sof(H49A)=Sof(H49B)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=
 Sof(H51B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C6(H6), C36(H36)
3.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C17(H17A,H17B), C19(H19A,H19B), C35(H35A,H35B), C47(H47A,H47B),
 C49(H49C,H49D), C49A(H49A,H49B)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C20(H20), C37(H37),
 C38(H38), C40(H40), C41(H41), C44(H44), C45(H45), C50(H50), C50A(H50A)
3.d X=CH2 refined with riding coordinates:
 C21(H21A,H21B), C51(H51C,H51D), C51A(H51A,H51B)
3.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              25719
_shelx_hkl_checksum              6747
_olex2_date_sample_data_collection 2018-01-19
_olex2_date_sample_submission    2018-01-16
_olex2_exptl_crystal_mounting_method "'in fomblin film on a micromount"
_olex2_submission_original_sample_id RA-203-006
_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 1.325
_oxdiff_exptl_absorpt_empirical_full_min 0.715