InI3-catalyzed polyene cyclization of allenes and its application in the total synthesis of seven abietane-type diterpenoids
Huo, Chen-Yu; Zheng, Tian-Lu; Dai, Wei-Hao; Zhang, Zi-Hao; Wang, Jin-Da; Zhu, Dao-Yong; Wang, Shao-Hua; Zhang, Xiao-Ming; Xu, Xue-Tao; Chemical Science  (2022) –; doi:10.1039/D2SC04229K

data_1567984
_publ_section_title
;
 InI3-catalyzed polyene cyclization of allenes and its application in the
 total synthesis of seven abietane-type diterpenoids
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04229K
_journal_year                    2022
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C22 H24'
_chemical_formula_sum            'C22 H24'
_chemical_formula_weight         288.41
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2bw5cs
_audit_creation_date             2021-12-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-06 deposited with the CCDC.	2022-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   17.4778(4)
_cell_length_b                   17.4778(4)
_cell_length_c                   9.9640(2)
_cell_measurement_reflns_used    9907
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.4540
_cell_measurement_theta_min      2.8870
_cell_volume                     2635.95(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.962
_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     45.00  85.00   0.50    0.45    --  107.75-125.00 -30.00   80
  2  \w     35.00  63.00   0.50    0.45    --  107.75 -57.00   0.00   56
  3  \w     36.00  61.00   0.50    0.45    --  107.75 -57.00 -30.00   50
  4  \w     59.00 122.00   0.50    0.45    --  107.75 150.00  96.00  126
  5  \w    128.00 166.00   0.50    0.45    --  107.75 150.00  96.00   76
  6  \w    -21.00  17.00   0.50    0.15    --   47.57 -19.00-180.00   76
  7  \w    -23.00  23.00   0.50    0.15    --   47.57 -19.00-150.00   92
  8  \w   -170.00 -80.00   0.50    0.45    -- -100.00-128.00-102.00  180
  9  \w    -99.00 -71.00   0.50    0.15    --  -47.57-146.00  70.00   56
 10  \w    -84.00 -58.00   0.50    0.15    --  -47.57 124.00 -45.00   52
 11  \w    -65.00 -27.00   0.50    0.45    -- -100.00 122.00 -65.00   76
 12  \w   -104.00 -72.00   0.50    0.45    -- -100.00 122.00 -65.00   64
 13  \w   -109.00 -82.00   0.50    0.45    -- -100.00 121.00 -84.00   54
 14  \w    -76.00 -28.00   0.50    0.45    -- -100.00 121.00 -84.00   96
 15  \w    -26.00  -1.00   0.50    0.15    --  -47.57   8.00 140.00   50
 16  \w     68.00  93.00   0.50    0.15    --   47.57 142.00 143.00   50
 17  \w     51.00  76.00   0.50    0.15    --   47.57   8.00 140.00   50
 18  \w   -128.00-103.00   0.50    0.45    -- -100.00  -8.00 -34.00   50
 19  \w    102.00 127.00   0.50    0.45    --  107.75 122.00 -65.00   50
 20  \w    132.00 158.00   0.50    0.45    --  107.75  57.00 -90.00   52
 21  \w   -104.00 -36.00   0.50    0.15    --  -47.57 -19.00-150.00  136
 22  \w    -61.00 -33.00   0.50    0.15    --  -47.57 -57.00-150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0419720000
_diffrn_orient_matrix_UB_12      0.1010538000
_diffrn_orient_matrix_UB_13      -0.0105775000
_diffrn_orient_matrix_UB_21      -0.0926061000
_diffrn_orient_matrix_UB_22      -0.0104167000
_diffrn_orient_matrix_UB_23      -0.0124400000
_diffrn_orient_matrix_UB_31      -0.0045823000
_diffrn_orient_matrix_UB_32      0.0061524000
_diffrn_orient_matrix_UB_33      0.1537465000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            14286
_diffrn_reflns_point_group_measured_fraction_full 0.846
_diffrn_reflns_point_group_measured_fraction_max 0.798
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.110
_diffrn_reflns_theta_min         2.919
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78165
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.090
_exptl_crystal_description       needle
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.133
_refine_diff_density_min         -0.143
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 910 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2980
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0690P)^2^+0.2275P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1093
_refine_ls_wR_factor_ref         0.1125
_reflns_Friedel_coverage         0.567
_reflns_Friedel_fraction_full    0.670
_reflns_Friedel_fraction_max     0.614
_reflns_number_gt                2805
_reflns_number_total             2980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04229k2.cif
_cod_data_source_block           huochenyu-wsh_1223_auto
_cod_original_cell_volume        2635.95(13)
_cod_database_code               1567984
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_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:
 C6(H6), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C12(H12A,H12B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C11(H11), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C20(H20), C22(H22)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 3.805
_oxdiff_exptl_absorpt_empirical_full_min 0.166