Enantioselective and collective total synthesis of pentacyclic 19-<i>nor</i>-clerodanes.
Zhang, Zhi-Mao; Zhang, Junliang; Cai, Quan; Chemical science 14 (2023) 12598–12605; doi:10.1039/d3sc04335e

data_1570173
_publ_section_title
;
 Enantioselective and collective total synthesis of pentacyclic
 19-<i>nor</i>-clerodanes.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              12598
_journal_page_last               12605
_journal_paper_doi               10.1039/d3sc04335e
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C19 H20 O6'
_chemical_formula_sum            'C19 H20 O6'
_chemical_formula_weight         344.35
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-05 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.68840(10)
_cell_length_b                   7.0394(2)
_cell_length_c                   35.4914(7)
_cell_measurement_reflns_used    15041
_cell_measurement_temperature    172.95(13)
_cell_measurement_theta_max      74.2130
_cell_measurement_theta_min      4.9280
_cell_volume                     1671.02(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.95(13)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -19.00  17.00   1.00    1.00    --    0.00  37.00 -60.00   36
  2  \w     47.00  74.00   1.00    1.00    --    0.00  37.00 120.00   27
  3  \w    -21.00   8.00   1.00    1.00    --    0.00  57.00-150.00   29
  4  \w    -89.00 -42.00   1.00    1.00    --    0.00 -57.00-120.00   47
  5  \w     25.00  51.00   1.00    1.00    --    0.00  57.00 -90.00   26
  6  \w    -19.00  79.00   1.00    1.00    --    0.00  37.00   0.00   98
  7  \w    -19.00  26.00   1.00    1.00    --    0.00  37.00 120.00   45
  8  \w    -25.00  56.00   1.00    1.00    --    0.00  77.00  30.00   81
  9  \w     39.00  85.00   1.00    1.00    --    0.00  37.00 -60.00   46
 10  \w    -39.00   8.00   1.00    1.00    --    0.00 -57.00-120.00   47
 11  \w     39.00  89.00   1.00    1.00    --    0.00  57.00-150.00   50
 12  \w    -23.00  18.00   1.00    1.00    --    0.00  57.00 -90.00   41
 13  \w     63.00  94.00   1.00    2.00    --   95.80  82.00-120.00   31
 14  \w     63.00 165.00   1.00    2.00    --   95.80  81.00 102.00  102
 15  \w    126.00 168.00   1.00    2.00    --   95.80  58.00-168.35   42
 16  \w    122.00 184.00   1.00    2.00    --   95.80  72.00 161.33   62
 17  \w     67.00  93.00   1.00    2.00    --   95.80  72.00 161.33   26
 18  \w     73.00 118.00   1.00    2.00    --   95.80  58.00-168.35   45
 19  \w    113.00 185.00   1.00    2.00    --   95.80  80.00  22.79   72
 20  \w    127.00 185.00   1.00    2.00    --   95.80  61.00-120.00   58
 21  \w     72.00 112.00   1.00    2.00    --   95.80  61.00-120.00   40
 22  \w     97.00 185.00   1.00    2.00    --   95.80  79.00 -42.68   88
 23  \w     65.00  90.00   1.00    2.00    --   95.80  77.00   0.00   25
 24  \w    129.00 155.00   1.00    2.00    --   95.80  77.00   0.00   26
 25  \w     63.00  89.00   1.00    2.00    --   95.80  82.00 -90.00   26
 26  \w    152.00 179.00   1.00    2.00    --   95.80  82.00 -90.00   27
 27  \w     63.00  96.00   1.00    2.00    --   95.80  82.00 120.00   33
 28  \w    114.00 185.00   1.00    2.00    --   95.80  82.00 120.00   71
 29  \w     65.00  90.00   1.00    2.00    --   95.80  77.00 -60.00   25
 30  \w    122.00 181.00   1.00    2.00    --   95.80  77.00 -60.00   59
 31  \w     36.00 128.00   1.00    2.00    --   95.80 -82.00 -30.00   92
 32  \w     66.00  91.00   1.00    2.00    --   95.80  77.00-150.00   25
 33  \w     64.00  91.00   1.00    2.00    --   95.80  79.00 -42.68   27
 34  \w     64.00 174.00   1.00    2.00    --   95.80  80.00-164.43  110
 35  \w     42.00 123.00   1.00    2.00    --   95.80 -82.00-150.00   81
 36  \w     75.00 106.00   1.00    2.00    --   95.80  45.00 -60.00   31
 37  \w     64.00  90.00   1.00    2.00    --   95.80  82.00 -30.00   26
 38  \w     82.00 124.00   1.00    2.00    --   95.80 -82.00 150.00   42
 39  \w    160.00 185.00   1.00    2.00    --   95.80  77.00  79.67   25
 40  \w     63.00  88.00   1.00    2.00    --   95.80  82.00   0.00   25
 41  \w     63.00  91.00   1.00    2.00    --   95.80  82.00  90.00   28
 42  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-120.00   25
 43  \w     65.00  90.00   1.00    2.00    --   95.80  77.00-180.00   25
 44  \w    151.00 177.00   1.00    2.00    --   95.80  61.00  60.00   26
 45  \w     18.00  44.00   1.00    2.00    --   95.80 -82.00 150.00   26
 46  \w     71.00 132.00   1.00    2.00    --   95.80  61.00  60.00   61
 47  \w     75.00 115.00   1.00    2.00    --   95.80  45.00 -30.00   40
 48  \w     65.00  91.00   1.00    2.00    --   95.80  77.00 -90.00   26
 49  \w     64.00  90.00   1.00    2.00    --   95.80  82.00  30.00   26
 50  \w     81.00 112.00   1.00    2.00    --   95.80  30.00 -60.00   31
 51  \w     75.00 101.00   1.00    2.00    --   95.80  45.00 -90.00   26
 52  \w    131.00 184.00   1.00    2.00    --   95.80  45.00 -90.00   53
 53  \w     75.00 183.00   1.00    2.00    --   95.80  45.00  30.00  108
 54  \w     65.00  94.00   1.00    2.00    --   95.80  77.00 -30.00   29
 55  \w     64.00  90.00   1.00    2.00    --   95.80  82.00-150.00   26
 56  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  60.00   26
 57  \w     71.00  97.00   1.00    2.00    --   95.80  61.00   0.00   26
 58  \w     71.00  96.00   1.00    2.00    --   95.80  61.00  90.00   25
 59  \w    105.00 134.00   1.00    2.00    --   95.80  61.00  90.00   29
 60  \w     63.00 103.00   1.00    2.00    --   95.80 -82.00-120.00   40
 61  \w     34.00 120.00   1.00    2.00    --   95.80 -77.00  60.00   86
 62  \w    150.00 175.00   1.00    2.00    --   95.80  82.00-120.00   25
 63  \w     65.00  91.00   1.00    2.00    --   95.80  77.00  79.67   26
 64  \w     74.00 169.00   1.00    2.00    --   95.80  50.00  88.10   95
 65  \w     64.00 106.00   1.00    2.00    --   95.80  80.00  22.79   42
 66  \w     73.00  98.00   1.00    2.00    --   95.80  52.00 173.56   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2095802000
_diffrn_orient_matrix_UB_12      0.0265903000
_diffrn_orient_matrix_UB_13      0.0172031000
_diffrn_orient_matrix_UB_21      0.0949863000
_diffrn_orient_matrix_UB_22      -0.0360142000
_diffrn_orient_matrix_UB_23      -0.0388984000
_diffrn_orient_matrix_UB_31      -0.0100278000
_diffrn_orient_matrix_UB_32      0.2142182000
_diffrn_orient_matrix_UB_33      -0.0086783000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1301
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            35120
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         4.984
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.849
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56447
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.128
_refine_diff_density_min         -0.133
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1105 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         2978
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0340
_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^)+(0.0388P)^2^+0.2264P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0857
_refine_ls_wR_factor_ref         0.0870
_reflns_Friedel_coverage         0.680
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2827
_reflns_number_total             2978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04335e2.cif
_cod_data_source_block           exp_3388
_cod_depositor_comments
'Adding full bibliography for 1570171--1570173.cif.'
_cod_database_code               1570173
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.750
_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.a Ternary CH refined with riding coordinates:
 C5(H5), C9(H9), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C10(H10A,H10B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4A)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              57477
_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 4.180
_oxdiff_exptl_absorpt_empirical_full_min 0.252