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_1567983
_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_formula_moiety         'C20 H30 O3'
_chemical_formula_sum            'C20 H30 O3'
_chemical_formula_weight         318.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2bw5fv
_audit_creation_date             2022-06-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-06-29 deposited with the CCDC.	2022-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.293(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.7444(7)
_cell_length_b                   6.0960(2)
_cell_length_c                   22.9960(6)
_cell_measurement_reflns_used    4658
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.3670
_cell_measurement_theta_min      3.6020
_cell_volume                     3453.97(18)
_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 1.5 (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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     98.00 174.00   0.50    0.05    --  107.75  57.00-180.00  152
  2  \w    133.00 168.00   0.50    0.05    --  107.75  37.00-150.00   70
  3  \w     99.00 124.00   0.50    0.05    --  107.75  37.00-150.00   50
  4  \w     95.00 168.00   0.50    0.05    --  107.75  35.00  88.00  146
  5  \w     36.00 116.00   0.50    0.05    --   47.57  35.00  88.00  160
  6  \w    -33.00  -8.00   0.50    0.05    --  -47.57  35.00  88.00   50
  7  \w    -57.00 -27.00   0.50    0.05    -- -100.00  77.00 120.00   60
  8  \w    -69.00 -33.00   0.50    0.05    -- -100.00  57.00  60.00   72
  9  \w    -69.00 -27.00   0.50    0.05    -- -100.00  77.00   0.00   84
 10  \w    -99.00 -73.00   0.50    0.05    -- -100.00  77.00   0.00   52
 11  \w    -69.00 -44.00   0.50    0.05    -- -100.00  57.00 -30.00   50
 12  \w    -66.00 -27.00   0.50    0.05    -- -100.00  57.00 -90.00   78
 13  \w    -69.00 -44.00   0.50    0.05    -- -100.00  57.00-150.00   50
 14  \w     61.00  96.00   0.50    0.05    --  107.75 -99.00 150.00   70
 15  \w   -123.00 -87.00   0.50    0.05    -- -100.00 -35.00 -68.00   72
 16  \w   -168.00-119.00   0.50    0.05    -- -100.00 -57.00   0.00   98
 17  \w   -110.00 -85.00   0.50    0.05    -- -100.00 -57.00   0.00   50
 18  \w   -106.00 -41.00   0.50    0.05    --  -47.57 -35.00 -68.00  130
 19  \w     -7.00  35.00   0.50    0.05    --   47.57 -37.00 120.00   84
 20  \w    -26.00  16.00   0.50    0.05    --   47.57 -19.00 150.00   84
 21  \w     41.00  95.00   0.50    0.05    --  107.75 -77.00 150.00  108
 22  \w     35.00  60.00   0.50    0.05    --  107.75 -57.00   0.00   50
 23  \w     35.00  63.00   0.50    0.05    --  107.75 -57.00 -60.00   56
 24  \w     36.00  62.00   0.50    0.05    --  107.75 -57.00-150.00   52
 25  \w     37.00  63.00   0.50    0.05    --  107.75 -57.00-180.00   52
 26  \w    -26.00   7.00   0.50    0.05    --   47.57 -35.00 -68.00   66
;
_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      0.0498968000
_diffrn_orient_matrix_UB_12      0.1123756000
_diffrn_orient_matrix_UB_13      0.0322482000
_diffrn_orient_matrix_UB_21      -0.0304466000
_diffrn_orient_matrix_UB_22      0.0194222000
_diffrn_orient_matrix_UB_23      0.0552654000
_diffrn_orient_matrix_UB_31      0.0222236000
_diffrn_orient_matrix_UB_32      -0.2255127000
_diffrn_orient_matrix_UB_33      0.0207697000
_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  0.0447
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            10868
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         3.588
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.632
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27677
_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    1.225
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.975
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.231
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     216
_refine_ls_number_reflns         3023
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.231
_refine_ls_R_factor_all          0.1083
_refine_ls_R_factor_gt           0.0943
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2859
_refine_ls_wR_factor_ref         0.3056
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2311
_reflns_number_total             3023
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04229k2.cif
_cod_data_source_block           huochy_1116_autored
_cod_database_code               1567983
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.868
_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. Restrained distances
 H1_$1-H2_$2
 2.2 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C3(H3A), C4(H4), C6(H6), C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B)
3.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C14(H14)
3.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3)
;
_shelx_res_checksum              74896
_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 2.760
_oxdiff_exptl_absorpt_empirical_full_min 0.495