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_1567982
_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 H26 O2'
_chemical_formula_sum            'C20 H26 O2'
_chemical_formula_weight         298.41
_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.cc2bw59q
_audit_creation_date             2021-11-22
_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                 92.8010(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.2191(2)
_cell_length_b                   11.57240(10)
_cell_length_c                   14.8457(2)
_cell_measurement_reflns_used    31891
_cell_measurement_temperature    301.82(11)
_cell_measurement_theta_max      76.0630
_cell_measurement_theta_min      4.3630
_cell_volume                     3469.50(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (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 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      301.82(11)
_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 0.975
_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     24.00  49.00   0.50    0.05    --   46.32  77.00 -60.00   50
  2  \w     28.00  54.00   0.50    0.05    --   50.00  75.00-166.88   52
  3  \w     36.00  79.00   0.50    0.05    --   46.32  31.00 -57.00   86
  4  \w     84.00 118.00   0.50    0.05    --   46.32  31.00 -57.00   68
  5  \w     26.00  52.00   0.50    0.05    --   46.32  77.00 150.00   52
  6  \w     15.00  42.00   0.50    0.05    --   42.00  87.00-131.59   54
  7  \w     13.00  38.00   0.50    0.05    --   42.00  90.00  82.37   50
  8  \w    -20.00   6.00   0.50    0.05    --   14.00 101.00 160.22   52
  9  \w    -10.00  20.00   0.50    0.05    --   22.00  96.00  95.60   60
 10  \w    -30.00  -4.00   0.50    0.05    --   10.00 111.00-106.40   52
 11  \w     14.00  40.00   0.50    0.05    --   42.00  88.00 -20.51   52
 12  \w     92.00 126.00   0.50    0.05    --   54.00  77.00 -51.87   68
 13  \w     43.00  76.00   0.50    0.05    --   66.00  77.00-153.79   66
 14  \w     31.00  61.00   0.50    0.05    --   54.00  77.00 -51.87   60
 15  \w     44.00  69.00   0.50    0.05    --   66.00  76.00 -65.26   50
 16  \w     44.00  69.00   0.50    0.05    --   66.00  76.00   0.21   50
 17  \w     42.00  81.00   0.50    0.05    --   62.00  74.00 -24.19   78
 18  \w     36.00  63.00   0.50    0.05    --   58.00  75.00  71.17   54
 19  \w     33.00  59.00   0.50    0.05    --   54.00  74.00  40.97   52
 20  \w     35.00  61.00   0.50    0.05    --   58.00  77.00 103.00   52
 21  \w     47.00  73.00   0.50    0.05    --   66.00  73.00 119.88   52
 22  \w     32.00  58.00   0.50    0.05    --   54.00  75.00 167.13   52
 23  \w     42.00  75.00   0.50    0.05    --   62.00  73.00 177.49   66
 24  \w     82.00 108.00   0.50    0.05    --   54.00  75.00 167.13   52
 25  \w    113.00 139.00   0.50    0.12    --  104.25  31.00 -57.00   52
 26  \w     75.00 101.00   0.50    0.12    --  104.25 -77.00  30.00   52
 27  \w     38.00  69.00   0.50    0.12    --  104.25 -61.00  90.00   62
 28  \w     36.00  69.00   0.50    0.12    --  104.25 -77.00  30.00   66
 29  \w    -27.00  17.00   0.50    0.05    --   46.32 -31.00 142.00   88
 30  \w     43.00  68.00   0.50    0.12    --  104.25 -61.00 -60.00   50
 31  \w     40.00  72.00   0.50    0.12    --  104.25 -61.00 -90.00   64
 32  \w     32.00  73.00   0.50    0.12    --  104.25 -61.00-180.00   82
 33  \w     37.00 106.00   0.50    0.12    --  104.25 -94.00 -90.00  138
 34  \w     65.00 109.00   0.50    0.12    --  104.25-125.00-180.00   88
 35  \w     59.00 112.00   0.50    0.12    --  104.25-125.00-150.00  106
 36  \w     70.00 102.00   0.50    0.12    --  104.25 -94.00-180.00   64
 37  \w     66.00 111.00   0.50    0.12    --  104.25-125.00 -90.00   90
 38  \w     68.00 102.00   0.50    0.12    --  104.25 -94.00-120.00   68
 39  \w     32.00  57.00   0.50    0.12    --  104.25-125.00 -90.00   50
 40  \w     48.00 104.00   0.50    0.12    --  104.25 -94.00 -30.00  112
 41  \w     49.00 112.00   0.50    0.12    --  104.25-125.00  90.00  126
 42  \w     30.00  94.00   0.50    0.05    --   46.32-125.00   0.00  128
 43  \w    -10.00  19.00   0.50    0.05    --  -46.32  31.00 -57.00   58
 44  \w    -69.00 -30.00   0.50    0.05    --  -46.32  77.00  30.00   78
 45  \w    -24.00  20.00   0.50    0.05    --  -46.32  77.00  30.00   88
 46  \w    -58.00 -29.00   0.50    0.12    -- -102.00  61.00-150.00   58
 47  \w    -91.00 -30.00   0.50    0.12    -- -102.00  77.00-180.00  122
 48  \w    -64.00 -39.00   0.50    0.05    --  -62.00 -77.00-162.38   50
 49  \w   -170.00 -76.00   0.50    0.12    --  -98.00 -77.00 -96.56  188
 50  \w   -166.00-139.00   0.50    0.12    --  -94.00 -76.00   7.60   54
 51  \w   -168.00-106.00   0.50    0.12    --  -98.00 -77.00 103.38  124
 52  \w   -100.00 -75.00   0.50    0.12    --  -98.00 -77.00 103.38   50
 53  \w   -107.00 -72.00   0.50    0.12    --  -94.00 -76.00 169.24   70
 54  \w    -78.00 -51.00   0.50    0.05    --  -74.00 -76.00  39.13   54
 55  \w   -135.00 -71.00   0.50    0.12    --  -94.00 -76.00   7.60  128
 56  \w   -163.00 -79.00   0.50    0.12    -- -102.00 -77.00   0.00  168
 57  \w   -101.00 -76.00   0.50    0.12    --  -98.00 -76.00 -78.02   50
 58  \w    -89.00 -63.00   0.50    0.12    --  -86.00 -76.00-120.93   52
 59  \w    -71.00 -40.00   0.50    0.05    --  -62.00 -75.00-124.50   62
 60  \w   -161.00-111.00   0.50    0.12    --  -98.00 -76.00 -78.02  100
 61  \w    -80.00 -54.00   0.50    0.05    --  -74.00 -74.00  16.12   52
 62  \w    -89.00 -64.00   0.50    0.12    --  -86.00 -75.00 130.63   50
 63  \w    -83.00 -52.00   0.50    0.05    --  -74.00 -75.00 141.83   62
 64  \w   -123.00 -97.00   0.50    0.05    --  -74.00 -75.00 141.83   52
 65  \w   -159.00-110.00   0.50    0.12    --  -86.00 -74.00  83.87   98
 66  \w   -158.00-102.00   0.50    0.12    --  -86.00 -75.00 130.63  112
 67  \w    -86.00 -60.00   0.50    0.12    --  -82.00 -74.00 102.47   52
 68  \w    -77.00 -52.00   0.50    0.05    --  -74.00 -74.00  52.66   50
 69  \w   -125.00 -68.00   0.50    0.12    --  -90.00 -74.00  42.45  114
 70  \w   -154.00-129.00   0.50    0.12    --  -90.00 -74.00  42.45   50
 71  \w   -159.00-117.00   0.50    0.12    --  -90.00 -74.00 112.66   84
 72  \w    -96.00 -70.00   0.50    0.12    --  -90.00 -74.00 112.66   52
 73  \w    -89.00 -64.00   0.50    0.12    --  -86.00 -74.00  83.87   50
 74  \w   -160.00 -70.00   0.50    0.12    --  -90.00 -73.00 -38.42  180
 75  \w    -83.00 -53.00   0.50    0.05    --  -74.00 -73.00 -67.17   60
 76  \w   -102.00 -69.00   0.50    0.12    --  -90.00 -73.00-159.89   66
 77  \w    -81.00 -55.00   0.50    0.05    --  -74.00 -73.00-166.11   52
 78  \w    -91.00 -65.00   0.50    0.12    --  -86.00 -73.00 -75.28   52
 79  \w    -91.00 -58.00   0.50    0.12    --  -78.00 -73.00 -42.81   66
 80  \w   -125.00 -99.00   0.50    0.05    --  -74.00 -73.00 -67.17   52
 81  \w   -166.00-114.00   0.50    0.12    --  -94.00 -72.00-176.28  104
 82  \w   -151.00-125.00   0.50    0.12    --  -86.00 -73.00 -75.28   52
 83  \w    -96.00 -63.00   0.50    0.12    --  -82.00 -72.00 -98.21   66
 84  \w    -98.00 -61.00   0.50    0.12    --  -82.00 -72.00   2.69   74
 85  \w    -96.00 -70.00   0.50    0.12    --  -90.00 -73.00  52.49   52
 86  \w    -91.00 -58.00   0.50    0.12    --  -78.00 -73.00 137.24   66
 87  \w    -80.00 -54.00   0.50    0.05    --  -74.00 -72.00 157.80   52
 88  \w   -162.00 -69.00   0.50    0.12    --  -90.00 -73.00  30.45  186
 89  \w    -88.00 -62.00   0.50    0.12    --  -82.00 -71.00 -17.98   52
 90  \w    -95.00 -70.00   0.50    0.12    --  -90.00 -70.00 -23.15   50
 91  \w    -99.00 -73.00   0.50    0.12    --  -94.00 -72.00-176.28   52
 92  \w    -75.00 -47.00   0.50    0.05    --  -66.00 -70.00-158.94   56
 93  \w    -76.00 -50.00   0.50    0.05    --  -70.00 -70.00-144.43   52
 94  \w    -99.00 -71.00   0.50    0.12    --  -90.00 -68.00-159.32   56
 95  \w   -162.00-106.00   0.50    0.12    --  -90.00 -68.00-159.32  112
 96  \w   -100.00 -71.00   0.50    0.12    --  -90.00 -68.00-137.55   58
 97  \w    -85.00 -59.00   0.50    0.12    --  -78.00 -67.00 -88.40   52
 98  \w   -100.00 -75.00   0.50    0.12    --  -94.00 -67.00 -84.00   50
 99  \w   -167.00 -76.00   0.50    0.12    --  -94.00 -66.00 -50.18  182
100  \w   -153.00-127.00   0.50    0.12    --  -90.00 -70.00 -23.15   52
101  \w   -167.00 -76.00   0.50    0.12    --  -94.00 -64.00-151.18  182
102  \w    -83.00 -57.00   0.50    0.05    --  -74.00 -65.00  67.55   52
103  \w   -114.00 -72.00   0.50    0.12    --  -90.00 -64.00 108.53   84
104  \w   -111.00 -79.00   0.50    0.12    --  -94.00 -65.00 143.08   64
105  \w   -174.00 -82.00   0.50    0.12    -- -102.00 -69.00 140.11  184
106  \w   -152.00-127.00   0.50    0.12    --  -90.00 -54.00  47.20   50
107  \w   -144.00 -77.00   0.50    0.12    --  -94.00 -63.00  70.77  134
108  \w   -119.00 -76.00   0.50    0.12    --  -90.00 -54.00  47.20   86
109  \w   -161.00-131.00   0.50    0.12    -- -102.00 -31.00 142.00   60
110  \w   -101.00 -76.00   0.50    0.05    --  -46.32 -31.00 142.00   50
111  \w    -70.00 -37.00   0.50    0.05    --  -46.32 -37.00  60.00   66
112  \w   -103.00 -74.00   0.50    0.12    --  -90.00 -61.00-121.27   58
113  \w   -154.00-126.00   0.50    0.12    --  -90.00 -61.00-121.27   56
114  \w    -73.00 -34.00   0.50    0.12    -- -102.00 125.00 -30.00   78
115  \w    -80.00 -29.00   0.50    0.12    -- -102.00 144.00  27.81  102
116  \w   -126.00-101.00   0.50    0.12    -- -102.00 144.00  27.81   50
117  \w   -112.00 -80.00   0.50    0.12    -- -102.00 125.00 -30.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0396932000
_diffrn_orient_matrix_UB_12      0.1076016000
_diffrn_orient_matrix_UB_13      -0.0313752000
_diffrn_orient_matrix_UB_21      0.0644659000
_diffrn_orient_matrix_UB_22      0.0586491000
_diffrn_orient_matrix_UB_23      -0.0270406000
_diffrn_orient_matrix_UB_31      -0.0092653000
_diffrn_orient_matrix_UB_32      -0.0521547000
_diffrn_orient_matrix_UB_33      -0.0952505000
_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  0.0362
_diffrn_reflns_av_unetI/netI     0.0136
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            53861
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.229
_diffrn_reflns_theta_min         4.379
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.559
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65659
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (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    1.143
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.037
_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     225
_refine_ls_number_reflns         3559
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0735P)^2^+0.7282P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1272
_refine_ls_wR_factor_ref         0.1319
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3108
_reflns_number_total             3559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04229k2.cif
_cod_data_source_block           huochenyu_1122_auto
_cod_database_code               1567982
_shelx_shelxl_version_number     2018/1
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C19)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: C5(0.3) H5A(0.3) H5B(0.3) H5C(0.3) C9(0.7) H9A(0.7) H9B(0.7)
 H9C(0.7) H15(0.7) H15A(0.3) C19(0.7) H19A(0.7) H19B(0.7) H19C(0.7) C21(0.3)
 H21A(0.3) H21B(0.3) H21C(0.3)
4.a Ternary CH refined with riding coordinates:
 C14(H14), C15(H15), C15(H15A)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C20(H20A,H20B)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C13(H13), C18(H18)
4.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              75286
_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 3.404
_oxdiff_exptl_absorpt_empirical_full_min 0.483