Divergent Total Syntheses of Five Illudalane Sesquiterpenes and Assignment of the Absolute Configuration
Zeng, Zhixiong; Zhao, Yifan; Zhang, Yandong; Chemical Communications  (2019) –; doi:10.1039/C9CC00933G

data_7123147
_publ_section_title
;
 Divergent Total Syntheses of Five Illudalane Sesquiterpenes and
 Assignment of the Absolute Configuration
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC00933G
_journal_year                    2019
_chemical_formula_moiety         'C22 H21 Br O4'
_chemical_formula_sum            'C22 H21 Br O4'
_chemical_formula_weight         429.30
_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_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-31 deposited with the CCDC.    2019-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.35275(17)
_cell_length_b                   12.5835(2)
_cell_length_c                   15.0399(3)
_cell_measurement_reflns_used    11305
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      62.0890
_cell_measurement_theta_min      4.2440
_cell_volume                     1959.31(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_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    -40.00  24.00   1.00    2.48    --   32.31 -38.00 -60.00   64
  2  \w     64.00 106.00   1.00   10.00    --   94.50  38.00  30.00   42
  3  \w    125.00 151.00   1.00   10.00    --   94.50  38.00  30.00   26
  4  \w    123.00 166.00   1.00   10.00    --   94.50  77.00  30.00   43
  5  \w    125.00 158.00   1.00   10.00    --   94.50  77.00 120.00   33
  6  \w    107.00 141.00   1.00   10.00    --   94.50  77.00  60.00   34
  7  \w    105.00 145.00   1.00   10.00    --   94.50  77.00  90.00   40
  8  \w    104.00 164.00   1.00   10.00    --   94.50  77.00   0.00   60
  9  \w    114.00 147.00   1.00   10.00    --   94.50  77.00 -30.00   33
 10  \w    112.00 164.00   1.00   10.00    --   94.50  77.00 -60.00   52
 11  \w    106.00 132.00   1.00   10.00    --   94.50  38.00-150.00   26
 12  \w    101.00 154.00   1.00   10.00    --   94.50  77.00-180.00   53
 13  \w    102.00 128.00   1.00   10.00    --   94.50  77.00 -90.00   26
 14  \w     68.00  94.00   1.00   10.00    --   94.50  64.00 -30.00   26
 15  \w     68.00 138.00   1.00   10.00    --   94.50  64.00 -60.00   70
 16  \w     68.00 153.00   1.00   10.00    --   94.50  64.00-120.00   85
 17  \w     68.00 165.00   1.00   10.00    --   94.50  64.00 -90.00   97
 18  \w     88.00 121.00   1.00   10.00    --   94.50 -64.00-180.00   33
 19  \w     69.00 130.00   1.00   10.00    --   94.50 -92.00 -90.00   61
 20  \w     79.00 135.00   1.00   10.00    --   94.50 -92.00   0.00   56
 21  \w     84.00 109.00   1.00   10.00    --   94.50 -92.00  60.00   25
 22  \w     87.00 127.00   1.00   10.00    --   94.50 -92.00 150.00   40
 23  \w     61.00  91.00   1.00   10.00    --   94.50 -38.00  30.00   30
 24  \w     55.00  81.00   1.00   10.00    --   94.50 -92.00  60.00   26
 25  \w     52.00  78.00   1.00   10.00    --   94.50 -92.00   0.00   26
 26  \w     22.00  70.00   1.00   10.00    --   94.50-112.00 120.00   48
 27  \w     37.00  68.00   1.00   10.00    --   94.50 -92.00 150.00   31
 28  \w     22.00  48.00   1.00   10.00    --   94.50 -38.00  30.00   26
 29  \w     23.00 100.00   1.00   10.00    --   94.50 -50.00 -30.00   77
 30  \w     66.00 153.00   1.00   10.00    --   94.50  38.00   0.00   87
 31  \w     68.00 106.00   1.00   10.00    --   94.50  64.00  90.00   38
 32  \w     65.00 150.00   1.00   10.00    --   94.50  38.00 150.00   85
 33  \w     68.00 160.00   1.00   10.00    --   94.50  64.00  60.00   92
 34  \w     68.00  94.00   1.00   10.00    --   94.50  64.00 150.00   26
 35  \w     68.00  93.00   1.00   10.00    --   94.50  64.00 120.00   25
 36  \w     68.00 112.00   1.00   10.00    --   94.50  64.00  30.00   44
 37  \w     61.00  87.00   1.00   10.00    --   94.50  77.00  30.00   26
 38  \w     61.00  90.00   1.00   10.00    --   94.50  77.00  60.00   29
 39  \w     61.00  91.00   1.00   10.00    --   94.50  77.00 120.00   30
 40  \w     61.00 152.00   1.00   10.00    --   94.50  77.00 150.00   91
 41  \w     61.00  87.00   1.00   10.00    --   94.50  77.00 -30.00   26
 42  \w     61.00  87.00   1.00   10.00    --   94.50  77.00 -60.00   26
 43  \w     61.00  97.00   1.00   10.00    --   94.50  77.00 -90.00   36
 44  \w     68.00 151.00   1.00   10.00    --   94.50  64.00-150.00   83
 45  \w     61.00  87.00   1.00   10.00    --   94.50  77.00-150.00   26
 46  \w     61.00  86.00   1.00   10.00    --   94.50  77.00-180.00   25
 47  \w     64.00 103.00   1.00   10.00    --   94.50  38.00-150.00   39
 48  \w     61.00 102.00   1.00   10.00    --   94.50  77.00-120.00   41
 49  \w     61.00  87.00   1.00   10.00    --   94.50  77.00   0.00   26
 50  \w     61.00  87.00   1.00   10.00    --   94.50  77.00  90.00   26
 51  \w     55.00  89.00   1.00    2.48    --   32.31 153.00 138.00   34
 52  \w     35.00 112.00   1.00    2.48    --   32.31 178.00   0.00   77
 53  \w    -40.00  60.00   1.00    2.48    --   32.31 -38.00 120.00  100
 54  \w     47.00  76.00   1.00    2.48    --   32.31 -99.00 120.00   29
 55  \w     23.00  71.00   1.00   10.00    --   94.50-112.00   0.00   48
 56  \w     25.00  90.00   1.00   10.00    --   94.50-112.00-150.00   65
 57  \w     61.00 120.00   1.00   10.00    --   94.50 -50.00-180.00   59
 58  \w     27.00  72.00   1.00   10.00    --   94.50 -64.00-180.00   45
 59  \w      3.00  32.00   1.00    2.48    --  -32.31-134.00 -77.87   29
 60  \w    -60.00 -18.00   1.00    2.48    --  -32.31 -57.00-150.00   42
 61  \w    -79.00 -12.00   1.00    2.48    --  -32.31 -57.00 -90.00   67
 62  \w    -87.00   1.00   1.00    2.48    --  -32.31 -77.00   0.00   88
 63  \w    -64.00 -10.00   1.00    2.48    --  -32.31 -77.00  90.00   54
 64  \w    -77.00 -10.00   1.00    2.48    --  -32.31 -57.00 150.00   67
 65  \w    -76.00 -10.00   1.00    2.48    --  -32.31 -57.00  90.00   66
 66  \w    -24.00  18.00   1.00    2.48    --   32.31 -99.00 120.00   42
 67  \w   -100.00  -1.00   1.00    2.48    --  -32.31 -38.00  30.00   99
 68  \w    -92.00 -31.00   1.00    2.48    --  -32.31 -57.00-120.00   61
 69  \w   -100.00 -68.00   1.00    2.48    --  -32.31 -57.00-150.00   32
 70  \w   -109.00 -73.00   1.00    2.48    --  -32.31-178.00-120.00   36
 71  \w   -112.00 -72.00   1.00    2.48    --  -32.31-178.00 -30.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1145400000
_diffrn_orient_matrix_UB_12      0.0528723000
_diffrn_orient_matrix_UB_13      -0.0481348000
_diffrn_orient_matrix_UB_21      -0.0694187000
_diffrn_orient_matrix_UB_22      0.0147922000
_diffrn_orient_matrix_UB_23      0.0897434000
_diffrn_orient_matrix_UB_31      0.0647728000
_diffrn_orient_matrix_UB_32      0.1094389000
_diffrn_orient_matrix_UB_33      0.0111352000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0731
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            26160
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        62.190
_diffrn_reflns_theta_max         62.190
_diffrn_reflns_theta_min         4.582
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47577
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.537
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1251 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     247
_refine_ls_number_reflns         3093
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0313
_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^)+(0.0469P)^2^+0.6007P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.734
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                3022
_reflns_number_total             3093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc00933g2.cif
_cod_data_source_block           exp_20218
_cod_database_code               7123147
_shelx_shelxl_version_number     2014/8
_shelx_estimated_absorpt_t_max   0.749
_shelx_estimated_absorpt_t_min   0.749
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     62.30
_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:
 C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C25(H25A,H25B), C36(H36A,H36B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C12(H12), C19(H19), C27(H27)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,H2AC)
;
_shelx_res_checksum              80116
_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 5.030
_oxdiff_exptl_absorpt_empirical_full_min 0.313