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_4038088
_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 H38 O5'
_chemical_formula_sum            'C25 H38 O5'
_chemical_formula_weight         418.55
_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             2018-01-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.877(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.878(7)
_cell_length_b                   17.626(8)
_cell_length_c                   20.717(10)
_cell_measurement_reflns_used    3352
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      20.18
_cell_measurement_theta_min      2.30
_cell_volume                     5020(4)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.0490
_diffrn_reflns_av_unetI/netI     0.0596
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24898
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.100
_diffrn_reflns_theta_max         25.100
_diffrn_reflns_theta_min         1.879
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6579
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0849 before and 0.0510 after correction.
The Ratio of minimum to maximum transmission is 0.8827.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            COLORLESS
_exptl_crystal_density_diffrn    1.108
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.309
_exptl_crystal_size_mid          0.265
_exptl_crystal_size_min          0.143
_refine_diff_density_max         0.163
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     576
_refine_ls_number_reflns         8905
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.1122
_refine_ls_R_factor_gt           0.0566
_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^)+(0.0670P)^2^+0.3534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1289
_refine_ls_wR_factor_ref         0.1567
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4868
_reflns_number_total             8905
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00022_si_002.cif
_cod_data_source_block           xb0490_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 4038084--4038097.cif.
;
_cod_database_code               4038088
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.977
_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
 C34-C036 = C36A-C34
 1.5 with sigma of 0.02
 C37A-C36A = C37B-C036
 1.3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C37A \\sim C36A \\sim C34: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C37B \\sim C036 \\sim C34: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Sof(H34A)=Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(C036)=Sof(H036)=1-FVAR(1)
 Sof(H34)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C36A)=Sof(H36A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C7(H7A), C9(H9), C13(H13), C15(H15), C16(H16), C32(H32), C34(H34), C34(H34A),
 C38(H38), C40(H40), C41(H41)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C14(H14A,H14B), C18(H18A,H18B), C22(H22A,H22B), C31(H31A,H31B),
 C39(H39A,H39B), C43(H43A,H43B), C47(H47A,H47B)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C36A(H36A), C036(H036)
5.d X=CH2 refined with riding coordinates:
 C11(H11A,H11B), C21(H21A,H21B), C37A(H37A,H37B), C46(H46A,H46B), C37B(H37C,
 H37D)
5.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C12(H12A,H12B,H12C), C20(H20A,H20B,H20C),
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,
 H28C), C35(H35A,H35B,H35C), C45(H45A,H45B,H45C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C)
5.f Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3), O7(H7), O8(H8)
;
_shelx_res_checksum              5869
_shelx_hkl_checksum              32278
_olex2_submission_special_instructions 'No special instructions were received'