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_4038086
_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         'C27 H42 O7'
_chemical_formula_sum            'C27 H42 O7'
_chemical_formula_weight         478.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.727(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.152(2)
_cell_length_b                   16.857(3)
_cell_length_c                   12.706(2)
_cell_measurement_reflns_used    826
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      18.21
_cell_measurement_theta_min      2.30
_cell_volume                     2683.2(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0801
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6680
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.098
_diffrn_reflns_theta_max         25.098
_diffrn_reflns_theta_min         2.025
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.084
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6705
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0669 before and 0.0473 after correction.
The Ratio of minimum to maximum transmission is 0.8995.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.324
_exptl_crystal_size_mid          0.258
_exptl_crystal_size_min          0.142
_refine_diff_density_max         0.525
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 889 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.1(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4507
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1257
_refine_ls_R_factor_gt           0.0773
_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^)+(0.1206P)^2^+0.5225P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1928
_refine_ls_wR_factor_ref         0.2310
_reflns_Friedel_coverage         0.887
_reflns_Friedel_fraction_full    0.889
_reflns_Friedel_fraction_max     0.889
_reflns_number_gt                2710
_reflns_number_total             4507
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00022_si_002.cif
_cod_data_source_block           xb0846_0m
_cod_depositor_comments
'Adding full bibliography for 4038084--4038097.cif.'
_cod_original_cell_volume        2683.3(8)
_cod_database_code               4038086
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.973
_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. Rigid bond restraints
 C5, C4, C1, C3, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C5 \\sim C2 \\sim C3 \\sim O1 \\sim O2: within 2A with sigma
of 0.001 and sigma for terminal atoms of 0.02
C14 \\sim C13 \\sim C12 \\sim C10 \\sim O5: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C7(H7A), C9(H9), C11(H11), C15(H15), C17(H17), C20(H20)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C8(H8A,H8B), C12(H12A,H12B), C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C14(H14)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C)
4.e Idealised tetrahedral OH refined as rotating group:
 O5(H5), O6(H6), O7(H7)
;
_shelx_res_checksum              72262
_shelx_hkl_checksum              15459
_olex2_submission_special_instructions 'No special instructions were received'