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_7133035
_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      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_Int_Tables_number      19
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-09
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2024-01-17 deposited with the CCDC.	2024-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.9015(1)
_cell_length_b                   11.1195(1)
_cell_length_c                   24.8315(3)
_cell_measurement_reflns_used    5707
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.3340
_cell_measurement_theta_min      3.5590
_cell_volume                     1905.60(4)
_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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9910
_diffrn_measured_fraction_theta_max 0.9762
_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    -13.00  72.00   0.50    0.36    --    0.00  57.00  60.00  170
  2  \w     43.00  69.00   0.50    0.36    --    0.00  20.00  13.00   52
  3  \w     -4.00  61.00   0.50    0.36    --    0.00  19.00-120.00  130
  4  \w     86.00 163.00   0.50    1.44    --   98.25  57.00   0.00  154
  5  \w    123.00 168.00   0.50    1.44    --   98.25  38.00  30.00   90
  6  \w    100.00 132.00   0.50    1.44    --   98.25  20.00  13.00   64
  7  \w     91.00 168.00   0.50    1.44    --   98.25  19.00 -60.00  154
  8  \w     44.00 104.00   0.50    1.44    --   98.25 -99.00-150.00  120
  9  \w     31.00  59.00   0.50    1.44    --   98.25 -99.00 -30.00   56
 10  \w     73.00 106.00   0.50    1.44    --   98.25 -99.00 -90.00   66
 11  \w     73.00 106.00   0.50    1.44    --   98.25 -99.00 -30.00   66
 12  \w     79.00 109.00   0.50    1.44    --   98.25-125.00 120.00   60
 13  \w     34.00 111.00   0.50    1.44    --   98.25-125.00 150.00  154
 14  \w     30.00  79.00   0.50    1.44    --   98.25 -99.00 150.00   98
 15  \w     72.00  98.00   0.50    1.44    --   98.25 -77.00 -30.00   52
 16  \w     27.00  62.00   0.50    1.44    --   98.25 -57.00  60.00   70
 17  \w     36.00  61.00   0.50    1.44    --   98.25 -57.00  30.00   50
 18  \w     33.00  60.00   0.50    1.44    --   98.25 -77.00 -30.00   54
 19  \w     27.00  57.00   0.50    1.44    --   98.25 -57.00 -30.00   60
 20  \w     51.00  98.00   0.50    1.44    --   98.25 -77.00-150.00   94
 21  \w    -38.00  -5.00   0.50    0.36    --    0.00 -20.00-153.00   66
 22  \w    -19.00   8.00   0.50    0.36    --    0.00 -38.00-180.00   54
 23  \w    -68.00 -39.00   0.50    0.36    --    0.00 -57.00 120.00   58
 24  \w    -31.00  -4.00   0.50    0.36    --    0.00 -57.00 120.00   54
 25  \w    -44.00 -19.00   0.50    1.44    --  -90.00  38.00  90.00   50
 26  \w    -65.00 -27.00   0.50    1.44    --  -90.00  57.00  90.00   76
 27  \w    -44.00 -18.00   0.50    1.44    --  -90.00  38.00  30.00   52
 28  \w    -44.00 -19.00   0.50    1.44    --  -90.00  38.00 -30.00   50
 29  \w    -47.00 -21.00   0.50    1.44    --  -90.00  77.00 -90.00   52
 30  \w    -44.00 -19.00   0.50    1.44    --  -90.00  38.00   0.00   50
 31  \w    -96.00 -68.00   0.50    1.44    --  -90.00  77.00 -90.00   56
 32  \w    -44.00 -19.00   0.50    1.44    --  -90.00  38.00-150.00   50
 33  \w    -63.00 -18.00   0.50    1.44    --  -90.00  57.00-150.00   90
 34  \w   -162.00 -83.00   0.50    1.44    --  -90.00 -20.00-153.00  158
 35  \w   -159.00 -90.00   0.50    1.44    --  -90.00 -99.00 -90.00  138
;
_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      -0.0602729000
_diffrn_orient_matrix_UB_12      -0.1328027000
_diffrn_orient_matrix_UB_13      0.0057924000
_diffrn_orient_matrix_UB_21      -0.2096995000
_diffrn_orient_matrix_UB_22      0.0333361000
_diffrn_orient_matrix_UB_23      -0.0151476000
_diffrn_orient_matrix_UB_31      0.0472924000
_diffrn_orient_matrix_UB_32      -0.0212292000
_diffrn_orient_matrix_UB_33      -0.0598674000
_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  0.0306
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.9910
_diffrn_reflns_Laue_measured_fraction_max 0.9762
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            20285
_diffrn_reflns_point_group_measured_fraction_full 0.9925
_diffrn_reflns_point_group_measured_fraction_max 0.9647
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         73.70
_diffrn_reflns_theta_min         3.56
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.656
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.386
_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            colorless
_exptl_crystal_colour_primary    colorless
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       prism
_exptl_crystal_F_000             770.451
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.1190
_refine_diff_density_min         -0.0825
_refine_diff_density_rms         0.0194
_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   0.02(4)
_refine_ls_d_res_high            0.8032
_refine_ls_d_res_low             12.4157
_refine_ls_extinction_coef       0.0011
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.1437
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     683
_refine_ls_number_reflns         3712
_refine_ls_number_restraints     600
_refine_ls_restrained_S_all      1.0449
_refine_ls_R_factor_all          0.0171
_refine_ls_R_factor_gt           0.0170
_refine_ls_shift/su_max          -0.0009
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0249P)^2^+0.0719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0433
_refine_ls_wR_factor_ref         0.0434
_reflns_Friedel_coverage         0.949
_reflns_limit_h_max              8
_reflns_limit_h_min              -8
_reflns_limit_k_max              13
_reflns_limit_k_min              -13
_reflns_limit_l_max              30
_reflns_limit_l_min              -30
_reflns_number_gt                3688
_reflns_number_total             3712
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4cc01462f2.cif
_cod_data_source_block           MER-2022-173-1
_cod_depositor_comments
'Adding full bibliography for 7133034--7133036.cif.'
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               7133035
_chemical_oxdiff_formula         'C84  H136  O16  '
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(H17b) \\sim Ueq, Uanis(H17a) \\sim Ueq, Uanis(H17c) \\sim Ueq: with sigma
of 0.002 and sigma for terminal atoms of 0.004
2. Rigid body (RIGU) restrains
 H1, O1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O3, C16, O4, C4, C17, C15, C5, C3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.004
 C4, C16, O4, O3, C17
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.004
 O3, O4, C2, C14, C7, C6, C15, C16, C5, C17, C9, C1, C3, C4, C8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 O4, C16, O3, C17, C4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 C12, C13, C11, C18, C19, C20, H12, H13a, H13b, H11a, H11b, H18, H19a, H19b,
 H19c, H20a, H20b, H20c, C10, H10a, H10b, C8, H8, C1, C21
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, C15, C3, C5, C6, C7, C2, C16
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.004
 C8, H8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H14a, H14b, H14c, C14
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C7, H14a, H7a, H7b
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C6, H6a, H6b
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C15, H15a, H15b, H15c
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5, H5a, H5b
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C17, H17a, H17b, H17c
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
;
_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 1.520
_oxdiff_exptl_absorpt_empirical_full_min 0.644