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_4129628
_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         'C29 H35 N O6 Si'
_chemical_formula_sum            'C29 H35 N O6 Si'
_chemical_formula_weight         521.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                68.764(9)
_cell_angle_beta                 78.415(8)
_cell_angle_gamma                85.076(9)
_cell_formula_units_Z            2
_cell_length_a                   7.3277(7)
_cell_length_b                   12.5761(16)
_cell_length_c                   16.8309(13)
_cell_measurement_reflns_used    3740
_cell_measurement_temperature    293
_cell_measurement_theta_max      26.8590
_cell_measurement_theta_min      4.1270
_cell_volume                     1416.1(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -53.00   35.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256  -38.0000  -30.0000 88

  2 omega  -20.00   55.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256  -99.0000  -60.0000 75

  3 omega  -11.00   83.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256   77.0000 -120.0000 94

  4 omega   -1.00   83.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256   57.0000  120.0000 84

  5 omega   -1.00   83.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256   57.0000  150.0000 84

  6 omega   35.00   88.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256  178.0000  120.0000 53

  7 omega  -58.00   -4.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -      -16.6631  104.0000  -41.0000 54

  8 omega  -53.00   19.00   1.0000   11.2400
omega____ theta____ kappa____ phi______ frames
    -       15.7256  -38.0000  120.0000 72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0281580000
_diffrn_orient_matrix_UB_12      -0.0532802000
_diffrn_orient_matrix_UB_13      0.0013247000
_diffrn_orient_matrix_UB_21      0.0087890000
_diffrn_orient_matrix_UB_22      -0.0247563000
_diffrn_orient_matrix_UB_23      0.0442271000
_diffrn_orient_matrix_UB_31      -0.0943152000
_diffrn_orient_matrix_UB_32      0.0145092000
_diffrn_orient_matrix_UB_33      0.0125323000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            17185
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.476
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.124
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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    1.223
_exptl_crystal_description
;
;
_exptl_crystal_F_000             556
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.7
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.268
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     340
_refine_ls_number_reflns         5779
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0891
_refine_ls_R_factor_gt           0.0610
_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^)+(0.0809P)^2^+0.3211P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1560
_refine_ls_wR_factor_ref         0.1806
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3934
_reflns_number_total             5779
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08958_si_006.cif
_cod_data_source_block           liubo-slq12059
_cod_database_code               4129628
_reflns_odcompleteness_completeness 99.76
_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
2. Rigid bond restraints
 O00U, N00S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3.a Ternary CH refined with riding coordinates:
 C00A(H00A), C00D(H00D), C00K(H00K)
3.b Secondary CH2 refined with riding coordinates:
 C00H(H00E,H00F), C00I(H00G,H00H), C00J(H00I,H00J), C00L(H00L,H00M)
3.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00T(H00Z), C00Y(H1AA), C010(H010), C011(H011)
3.d Idealised Me refined as rotating group:
 C00M(H00N,H00O,H00P), C00O(H00Q,H00R,H00S), C00Q(H00T,H00U,H00V), C00R(H00W,
 H00X,H00Y), C00W(H00,H,HA), C00X(H0AA,HB,HC)
;
_shelx_res_checksum              91104
_shelx_hkl_checksum              17988
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'