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_4129629
_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         'C23 H26 O3'
_chemical_formula_sum            'C23 H26 O3'
_chemical_formula_weight         350.44
_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     direct
_audit_creation_date             2014-12-31
_audit_creation_method
;
Olex2 1.2
(compiled 2014.12.26 svn.r3119 for OlexSys, GUI svn.r4975)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.882(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6632(3)
_cell_length_b                   14.6384(4)
_cell_length_c                   11.1116(3)
_cell_measurement_reflns_used    5695
_cell_measurement_temperature    293
_cell_measurement_theta_max      71.8460
_cell_measurement_theta_min      4.9160
_cell_volume                     1853.14(10)
_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, 2008)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.951
_diffrn_measurement_details
;
  1 omega  -52.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000   30.0000 87

  2 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486 -125.0000 -180.0000 67

  3 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486 -125.0000 -120.0000 67

  4 omega  -36.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486  -34.0000  107.0000 95

  5 omega   13.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486   38.0000    0.0000 93

  6 omega   13.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486   38.0000 -150.0000 93

  7 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486 -125.0000  -30.0000 67

  8 omega  -33.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486  -57.0000 -120.0000 87

  9 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486 -125.0000   30.0000 67

 10 omega  -33.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486  -57.0000   30.0000 87

 11 omega   17.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486   57.0000  -90.0000 87

 12 omega  -33.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.5486  -57.0000  -30.0000 87

 13 omega   38.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -60.0000 71

 14 omega   37.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 54

 15 omega   38.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 60

 16 omega   38.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 60

 17 omega   37.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 54

 18 omega   39.00  137.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 98

 19 omega   37.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 54

 20 omega   37.00  115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 78

 21 omega   37.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 54

 22 omega   38.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 71

 23 omega   38.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 71

 24 omega   37.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 54

 25 omega   38.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 60

 26 omega   37.00   62.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 25
;
_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      -0.0579206000
_diffrn_orient_matrix_UB_12      -0.0050706000
_diffrn_orient_matrix_UB_13      -0.1538796000
_diffrn_orient_matrix_UB_21      -0.0069706000
_diffrn_orient_matrix_UB_22      -0.1048108000
_diffrn_orient_matrix_UB_23      0.0073547000
_diffrn_orient_matrix_UB_31      -0.1219708000
_diffrn_orient_matrix_UB_32      0.0084351000
_diffrn_orient_matrix_UB_33      -0.0018810000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0332
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            14290
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.044
_diffrn_reflns_theta_min         3.880
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.647
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30280
_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 yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description
;
;
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.239
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3468
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0572
_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^)+(0.1036P)^2^+0.3179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1537
_refine_ls_wR_factor_ref         0.1596
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3048
_reflns_number_total             3468
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08958_si_011.cif
_cod_data_source_block           lb-slq-pq
_cod_original_cell_volume        1853.14(9)
_cod_database_code               4129629
_reflns_odcompleteness_completeness 97.28
_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.a Ternary CH refined with riding coordinates:
 C006(H006), C00D(H00E), C00L(H00N)
2.b Secondary CH2 refined with riding coordinates:
 C00F(H00F,H00G), C00G(H00H,H00I), C00I(H00K,H00L), C00M(H00O,H00P)
2.c Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00H(H00J), C00K(H00M), C00O(H00T), C00P(H00U)
2.d Idealised Me refined as rotating group:
 C00C(H00B,H00C,H00D), C00N(H00Q,H00R,H00S), C00Q(H00V,H00W,H00X)
2.e Idealised tetrahedral OH refined as rotating group:
 O002(H002)
;
_shelx_res_checksum              74088
_shelx_hkl_checksum              23507
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'