9-Step synthesis of (-)-larikaempferic acid methyl ester enabled by skeletal rearrangement.
Rivera, Mario E.; Li, Lei; Kolisetti, Aditya; Chi, Nina; Dai, Mingji; Chemical communications (Cambridge, England) 60 (2024) 7164–7167; doi:10.1039/d4cc01462f

data_7133036
_publ_section_title
;
 9-Step synthesis of (-)-larikaempferic acid methyl ester enabled by
 skeletal rearrangement.
;
_journal_issue                   56
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7164
_journal_page_last               7167
_journal_paper_doi               10.1039/d4cc01462f
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H34 O4'
_chemical_formula_sum            'C21 H34 O4'
_chemical_formula_weight         350.502
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_symmetry_Int_Tables_number      5
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-17
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.11.24 svn.r209d9fb2 for OlexSys, GUI svn.r6869)
;
_audit_update_record
;
2024-01-17 deposited with the CCDC.	2024-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.026(1)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.0209(2)
_cell_length_b                   6.9482(1)
_cell_length_c                   29.3036(2)
_cell_measurement_reflns_used    18479
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      72.4140
_cell_measurement_theta_min      3.1370
_cell_volume                     3897.74(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.02(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9951
_diffrn_measured_fraction_theta_max 0.9449
_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    -58.00 -19.00   0.50    0.50    --  -91.75  57.00   0.00   78
  2  \w    -63.00 -21.00   0.50    0.50    --  -91.75  57.00 -30.00   84
  3  \w    -64.00 -26.00   0.50    0.50    --  -91.75  57.00 -60.00   76
  4  \w    -44.00 -18.00   0.50    0.50    --  -91.75  38.00 -90.00   52
  5  \w    -65.00 -20.00   0.50    0.50    --  -91.75  57.00 -90.00   90
  6  \w    -20.00  27.00   0.50    0.25    --  -47.44  18.00-174.00   94
  7  \w    -30.00  21.00   0.50    0.25    --  -47.44  19.00 -30.00  102
  8  \w   -103.00 -77.00   0.50    0.50    --  -91.75 -18.00  17.00   52
  9  \w    -94.00 -68.00   0.50    0.50    --  -91.75 -77.00 -60.00   52
 10  \w    -93.00 -68.00   0.50    0.50    --  -91.75 -77.00 -30.00   50
 11  \w    -95.00 -69.00   0.50    0.50    --  -91.75 -77.00   0.00   52
 12  \w   -164.00 -99.00   0.50    0.50    --  -91.75 -77.00 -30.00  130
 13  \w   -146.00-120.00   0.50    0.50    --  -91.75 -77.00 -60.00   52
 14  \w   -143.00-118.00   0.50    0.50    --  -91.75 -74.00-104.29   50
 15  \w   -155.00-119.00   0.50    0.50    --  -91.75 -72.00-143.88   72
 16  \w   -164.00 -68.00   0.50    0.50    --  -91.75 -77.00-120.00  192
 17  \w    -96.00 -70.00   0.50    0.50    --  -91.75 -72.00-143.88   52
 18  \w    -94.00 -69.00   0.50    0.50    --  -91.75 -77.00 -90.00   50
 19  \w    -94.00 -69.00   0.50    0.50    --  -91.75 -74.00-104.29   50
 20  \w   -113.00 -75.00   0.50    0.50    --  -91.75 -67.00-123.88   76
 21  \w    -97.00 -72.00   0.50    0.50    --  -91.75 -66.00-121.93   50
 22  \w    -98.00 -73.00   0.50    0.50    --  -91.75 -64.00-146.34   50
 23  \w   -100.00 -75.00   0.50    0.50    --  -91.75 -64.00 -65.34   50
 24  \w    -97.00 -72.00   0.50    0.50    --  -91.75 -67.00 -38.76   50
 25  \w    -98.00 -73.00   0.50    0.50    --  -91.75 -64.00 -35.53   50
 26  \w    -95.00 -70.00   0.50    0.50    --  -91.75 -71.00 -19.59   50
 27  \w   -103.00 -77.00   0.50    0.50    --  -91.75 -59.00 -63.55   52
 28  \w    -98.00 -73.00   0.50    0.50    --  -91.75 -63.00 -96.52   50
 29  \w   -101.00 -76.00   0.50    0.50    --  -91.75 -58.00 -94.61   50
 30  \w   -101.00 -76.00   0.50    0.50    --  -91.75 -59.00 -68.95   50
 31  \w   -100.00 -75.00   0.50    0.50    --  -91.75 -58.00 -79.70   50
 32  \w   -162.00 -77.00   0.50    0.50    --  -91.75 -58.00 -98.91  170
 33  \w   -164.00-139.00   0.50    0.50    --  -91.75 -59.00 -63.55   50
 34  \w   -148.00-122.00   0.50    0.50    --  -91.75 -59.00 -68.95   52
 35  \w   -164.00-129.00   0.50    0.50    --  -91.75 -67.00 -38.76   70
 36  \w   -147.00 -76.00   0.50    0.50    --  -91.75 -52.00 -30.19  142
 37  \w   -102.00 -77.00   0.50    0.50    --  -91.75 -47.00 -76.92   50
 38  \w   -137.00-111.00   0.50    0.50    --  -91.75 -18.00  17.00   52
 39  \w   -121.00 -36.00   0.50    0.25    --  -47.44 -18.00  17.00  170
 40  \w    -66.00 -24.00   0.50    0.25    --  -47.44 -77.00 -60.00   84
 41  \w    -66.00 -25.00   0.50    0.25    --  -47.44 -77.00 -90.00   82
 42  \w    -54.00 -27.00   0.50    0.25    --  -47.44 -77.00-150.00   54
 43  \w    -69.00 -39.00   0.50    0.25    --  -47.44 -38.00 -60.00   60
 44  \w     31.00  57.00   0.50    0.25    --   47.44  57.00-120.00   52
 45  \w     54.00 103.00   0.50    0.25    --   47.44  18.00-174.00   98
 46  \w     92.00 130.00   0.50    0.50    --   99.41  18.00-174.00   76
 47  \w     29.00  93.00   0.50    0.50    --   99.41 -77.00-180.00  128
 48  \w    -19.00  11.00   0.50    0.25    --   47.44 -19.00-120.00   60
 49  \w     78.00 104.00   0.50    0.50    --   99.41 -99.00 -60.00   52
 50  \w     27.00  65.00   0.50    0.50    --   99.41 -57.00  90.00   76
 51  \w     -7.00  18.00   0.50    0.25    --   47.44 -18.00  17.00   50
;
_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      0.0743808000
_diffrn_orient_matrix_UB_12      0.0102851000
_diffrn_orient_matrix_UB_13      -0.0050980000
_diffrn_orient_matrix_UB_21      -0.0289094000
_diffrn_orient_matrix_UB_22      -0.0523950000
_diffrn_orient_matrix_UB_23      -0.0532571000
_diffrn_orient_matrix_UB_31      -0.0106284000
_diffrn_orient_matrix_UB_32      0.2150949000
_diffrn_orient_matrix_UB_33      -0.0126807000
_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  0.0421
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.9951
_diffrn_reflns_Laue_measured_fraction_max 0.9449
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            27039
_diffrn_reflns_point_group_measured_fraction_full 0.9682
_diffrn_reflns_point_group_measured_fraction_max 0.9065
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         72.49
_diffrn_reflns_theta_min         3.15
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.642
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.651
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       needle
_exptl_crystal_F_000             1540.902
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.1021
_refine_diff_density_min         -0.1197
_refine_diff_density_rms         0.0252
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.09(6)
_refine_ls_d_res_high            0.8084
_refine_ls_d_res_low             14.0107
_refine_ls_goodness_of_fit_ref   1.0913
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     1063
_refine_ls_number_reflns         7025
_refine_ls_number_restraints     1099
_refine_ls_restrained_S_all      1.0029
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0250
_refine_ls_shift/su_max          -0.0010
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0287P)^2^+0.1256P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0589
_refine_ls_wR_factor_ref         0.0593
_reflns_Friedel_coverage         0.861
_reflns_limit_h_max              23
_reflns_limit_h_min              -24
_reflns_limit_k_max              8
_reflns_limit_k_min              -7
_reflns_limit_l_max              35
_reflns_limit_l_min              -35
_reflns_number_gt                6841
_reflns_number_total             7025
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4cc01462f2.cif
_cod_data_source_block           MER-2022-137-3
_cod_depositor_comments
'Adding full bibliography for 7133034--7133036.cif.'
_cod_original_sg_symbol_Hall     ' I 2y'
_cod_database_code               7133036
_chemical_oxdiff_formula         'C168  H272  O32  '
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 O2', O1', C1', H1', C10', C2', C8', C11', H10a, H10b, C3', C7', C14', C9',
 H8', C21', C12', H11a, H11b, C4', H3', C6', H7'a, H7'b, H14a, H14b, H14c, H9'a,
  H9'b, C13', C18', H12', C15', C5', C16', H6'a, H6'b, H13a, H13b, C19', C20',
 H18', H15a, H15b, H15c, H5'a, H5'b, O3', O4', H19a, H19b, H19c, H20a, H20b,
 H20c, C17', H17a, H17b, H17c
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C16, O1, C1, H1, C2, C10, C8, C3, C7, C14, C11, H10c, H10d, H8, C9, C21, C4,
 H3, C6, H7a, H7b, H14d, H14e, H14f, C12, H11c, H11d, H9a, H9b, O2, C13, C5,
 C15, H6a, H6b, C18, H12, H13c, H13d, H5a, H5b, H15d, H15e, H15f, O4, O3, C19,
 C20, H18, C17, H19d, H19e, H19f, H20d, H20e, H20f, H17d, H17e, H17f
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         PBE
   BASIS SET:      def2-SVP
   CHARGE:         0
   MULTIPLICITY:   1
   SOLVATION:      Ethanol
   DATE:           2022-09-09_15-21-08
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone'
_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 1.226
_oxdiff_exptl_absorpt_empirical_full_min 0.838