Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access to Multi-Stereocenter Cyclohexanes from a Phenol.
Tong, Guanghu; Ding, Zhengwei; Liu, Zhi; Ding, You-Song; Xu, Liang; Zhang, Hailong; Li, Pengfei; The Journal of organic chemistry 85 (2020) 4813–4837; doi:10.1021/acs.joc.0c00022

data_4038087
_publ_section_title
;
 Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access
 to Multi-Stereocenter Cyclohexanes from a Phenol.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4813
_journal_page_last               4837
_journal_paper_doi               10.1021/acs.joc.0c00022
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C25 H42 O5 Si'
_chemical_formula_sum            'C25 H42 O5 Si'
_chemical_formula_weight         450.67
_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
_audit_creation_date             2017-09-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                69.414(7)
_cell_angle_beta                 79.030(7)
_cell_angle_gamma                68.150(7)
_cell_formula_units_Z            2
_cell_length_a                   9.5936(12)
_cell_length_b                   11.1608(15)
_cell_length_c                   14.6705(18)
_cell_measurement_reflns_used    5779
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      24.52
_cell_measurement_theta_min      2.29
_cell_volume                     1361.7(3)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17526
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.187
_diffrn_reflns_theta_max         25.187
_diffrn_reflns_theta_min         1.486
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.115
_exptl_absorpt_correction_T_max  0.9378
_exptl_absorpt_correction_T_min  0.8194
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.099
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             492
_exptl_crystal_size_max          0.532
_exptl_crystal_size_mid          0.254
_exptl_crystal_size_min          0.167
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4775
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0634P)^2^+0.4706P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3631
_reflns_number_total             4775
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00022_si_002.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 4038084--4038097.cif.'
_cod_database_code               4038087
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.941
_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
 C2-C1
 1.5 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C11(H11), C13(H13), C14(H14), C15(H15), C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C19(H19A,H19B), C6(H6A,H6B)
3.c Aromatic/amide H refined with riding coordinates:
 C9(H9)
3.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
3.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C16(H16A,H16B,H16C), C10(H10A,H10B,H10C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C21(H21A,H21B,H21C), C1(H1A,H1B,H1C), C17(H17A,
 H17B,H17C), C25(H25A,H25B,H25C)
3.f Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              94771
_shelx_hkl_checksum              40085
_olex2_submission_special_instructions 'No special instructions were received'