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_1570172
_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 H18 O6'
_chemical_formula_sum            'C19 H18 O6'
_chemical_formula_weight         342.33
_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             2023-06-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-26 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                   6.95740(10)
_cell_length_b                   10.4076(2)
_cell_length_c                   22.6105(4)
_cell_measurement_reflns_used    12236
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      73.9970
_cell_measurement_theta_min      4.6620
_cell_volume                     1637.22(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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  82.00   1.00    1.00    --    0.00  82.00 -90.00   55
  2  \w    -88.00 -45.00   1.00    1.00    --    0.00 -37.00 -30.00   43
  3  \w    -81.00 -27.00   1.00    1.00    --    0.00 -19.00-150.00   54
  4  \w    -32.00  15.00   1.00    1.00    --    0.00  82.00 -90.00   47
  5  \w    -88.00  30.00   1.00    1.00    --    0.00 -82.00-150.00  118
  6  \w    -13.00  15.00   1.00    1.00    --    0.00  37.00 -90.00   28
  7  \w     47.00  88.00   1.00    1.00    --    0.00  57.00  30.00   41
  8  \w     -9.00  22.00   1.00    1.00    --    0.00 -19.00-150.00   31
  9  \w     54.00  80.00   1.00    1.00    --    0.00  37.00 -90.00   26
 10  \w    -23.00  11.00   1.00    1.00    --    0.00  57.00  60.00   34
 11  \w     -7.00  19.00   1.00    1.00    --    0.00 -37.00 -30.00   26
 12  \w    -15.00  11.00   1.00    1.00    --    0.00  57.00  30.00   26
 13  \w    -53.00  11.00   1.00    1.00    --    0.00 -77.00  90.00   64
 14  \w    -88.00 -63.00   1.00    1.00    --    0.00 -77.00  90.00   25
 15  \w     28.00  73.00   1.00    1.00    --    0.00  57.00  60.00   45
 16  \w     35.00 127.00   1.00    1.00    --   95.80 -82.00-180.00   92
 17  \w    104.00 185.00   1.00    1.00    --   95.80  66.00 163.34   81
 18  \w     66.00 102.00   1.00    1.00    --   95.80  75.00-153.15   36
 19  \w     69.00  95.00   1.00    1.00    --   95.80  66.00 163.34   26
 20  \w    123.00 184.00   1.00    1.00    --   95.80  75.00  49.33   61
 21  \w    119.00 183.00   1.00    1.00    --   95.80  82.00 108.69   64
 22  \w     67.00 115.00   1.00    1.00    --   95.80  72.00  88.60   48
 23  \w      7.00 125.00   1.00    1.00    --   95.80 -82.00 -60.00  118
 24  \w     75.00 107.00   1.00    1.00    --   95.80  45.00 -30.00   32
 25  \w     75.00 148.00   1.00    1.00    --   95.80  45.00  60.00   73
 26  \w      6.00 100.00   1.00    1.00    --   95.80 -61.00-180.00   94
 27  \w     72.00  98.00   1.00    1.00    --   95.80  61.00 120.00   26
 28  \w     65.00 108.00   1.00    1.00    --   95.80  77.00  60.00   43
 29  \w     74.00 146.00   1.00    1.00    --   95.80  61.00 -30.00   72
 30  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 31  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-180.00   26
 32  \w     76.00 105.00   1.00    1.00    --   95.80  45.00  30.00   29
 33  \w     66.00  93.00   1.00    1.00    --   95.80  75.00  49.33   27
 34  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 35  \w      6.00 113.00   1.00    1.00    --   95.80 -82.00  90.00  107
 36  \w     65.00  91.00   1.00    1.00    --   95.80  76.00  -1.15   26
 37  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 108.69   26
 38  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-150.00   26
 39  \w     66.00  92.00   1.00    1.00    --   95.80  77.00  90.00   26
 40  \w     64.00  96.00   1.00    1.00    --   95.80  82.00   0.00   32
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-180.00   26
 42  \w     75.00 179.00   1.00    1.00    --   95.80  45.00 -60.00  104
 43  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 44  \w    111.00 178.00   1.00    1.00    --   95.80  45.00  30.00   67
 45  \w     78.00 175.00   1.00    1.00    --   95.80  45.00 150.00   97
 46  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -90.00   26
 47  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 48  \w     76.00 121.00   1.00    1.00    --   95.80  45.00 -90.00   45
 49  \w     63.00 102.00   1.00    1.00    --   95.80  82.00-150.00   39
 50  \w    110.00 147.00   1.00    1.00    --   95.80  45.00 -30.00   37
 51  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 52  \w     41.00 124.00   1.00    1.00    --   95.80 -82.00   0.00   83
 53  \w     65.00  91.00   1.00    1.00    --   95.80  82.00 -30.00   26
 54  \w     66.00  92.00   1.00    1.00    --   95.80  74.00  32.22   26
 55  \w      9.00  82.00   1.00    1.00    --   95.80 -61.00  90.00   73
 56  \w     76.00 122.00   1.00    1.00    --   95.80  30.00 -90.00   46
 57  \w    131.00 185.00   1.00    1.00    --   95.80  61.00-180.00   54
 58  \w    134.00 159.00   1.00    1.00    --   95.80  82.00-120.00   25
 59  \w     64.00  90.00   1.00    1.00    --   95.80  82.00  60.00   26
 60  \w     72.00  98.00   1.00    1.00    --   95.80  61.00-180.00   26
 61  \w     71.00  96.00   1.00    1.00    --   95.80  61.00 150.00   25
 62  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-120.00   26
 63  \w     73.00  99.00   1.00    1.00    --   95.80  52.00 171.84   26
 64  \w    160.00 185.00   1.00    1.00    --   95.80  72.00  88.60   25
 65  \w    128.00 153.00   1.00    1.00    --   95.80  59.00 -69.76   25
 66  \w     71.00  97.00   1.00    1.00    --   95.80  59.00 -69.76   26
;
_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      0.1031133000
_diffrn_orient_matrix_UB_12      -0.1069804000
_diffrn_orient_matrix_UB_13      -0.0347969000
_diffrn_orient_matrix_UB_21      0.0487254000
_diffrn_orient_matrix_UB_22      -0.0686978000
_diffrn_orient_matrix_UB_23      0.0584559000
_diffrn_orient_matrix_UB_31      -0.1898724000
_diffrn_orient_matrix_UB_32      -0.0756989000
_diffrn_orient_matrix_UB_33      -0.0038960000
_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  0.0960
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            34313
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         3.910
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.866
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34222
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.389
_exptl_crystal_description       plate
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.119
_refine_diff_density_min         -0.136
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1100 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.15(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         2912
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0421P)^2^+0.1848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0847
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2765
_reflns_number_total             2912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04335e2.cif
_cod_data_source_block           exp_2245
_cod_depositor_comments
'Adding full bibliography for 1570171--1570173.cif.'
_cod_database_code               1570172
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.746
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C5(H5), C9(H9), C11(H11), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C10(H10A,H10B), C16(H16A,H16B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              29650
_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 2.143
_oxdiff_exptl_absorpt_empirical_full_min 0.385