Total Synthesis of Atisane-Type Diterpenoids: Application of Diels-Alder Cycloadditions of Podocarpane-Type Unmasked ortho-Benzoquinones.
Song, Liqiang; Zhu, Guili; Liu, Yongjiang; Liu, Bo; Qin, Song; Journal of the American Chemical Society 137 (2015) 13706–13714; doi:10.1021/jacs.5b08958

data_4129639
_publ_section_title
;
 Total Synthesis of Atisane-Type Diterpenoids: Application of Diels-Alder
 Cycloadditions of Podocarpane-Type Unmasked ortho-Benzoquinones.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13706
_journal_page_last               13714
_journal_paper_doi               10.1021/jacs.5b08958
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C24 H38 O4 Si'
_chemical_formula_sum            'C24 H38 O4 Si'
_chemical_formula_weight         418.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-06-19
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4720)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.818(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3873(4)
_cell_length_b                   16.6013(8)
_cell_length_c                   19.9640(10)
_cell_measurement_reflns_used    7495
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.1370
_cell_measurement_theta_min      3.3230
_cell_volume                     2412.5(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 16.0874
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -69.00  -44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.5174 -178.0000 -180.0000 25

  2 omega  -24.00   24.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.5174  -99.0000   60.0000 48

  3 omega  -21.00   21.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.5174  -99.0000 -120.0000 42

  4 omega  -23.00    3.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.5174  -99.0000    0.0000 26

  5 omega   37.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       19.2361  178.0000   90.0000 58

  6 omega   -6.00   83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       19.2361   38.0000 -120.0000 89

  7 omega  -43.00   63.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       19.2361  -19.0000   30.0000 106
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0673157000
_diffrn_orient_matrix_UB_12      -0.0302153000
_diffrn_orient_matrix_UB_13      0.0095158000
_diffrn_orient_matrix_UB_21      0.0428774000
_diffrn_orient_matrix_UB_22      0.0245143000
_diffrn_orient_matrix_UB_23      0.0272654000
_diffrn_orient_matrix_UB_31      -0.0559086000
_diffrn_orient_matrix_UB_32      -0.0175957000
_diffrn_orient_matrix_UB_33      0.0216210000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            17944
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.056
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.123
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76680
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.153
_exptl_crystal_description
;
;
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4933
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0456
_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^)+(0.0565P)^2^+0.4825P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1121
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3681
_reflns_number_total             4933
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08958_si_001.cif
_cod_data_source_block           140616_s3_slq_m
_cod_database_code               4129639
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         C12h10o3n3
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.964
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C8(H8), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C10(H10A,H10B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C20(H20)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              61356
_shelx_hkl_checksum              25281