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_4038095
_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 H38 N2 O4'
_chemical_formula_sum            'C27 H38 N2 O4'
_chemical_formula_weight         454.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-08-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.677(2)
_cell_angle_gamma                90
_cell_formula_units_Z            32
_cell_length_a                   32.983(5)
_cell_length_b                   19.298(3)
_cell_length_c                   31.320(4)
_cell_measurement_reflns_used    9881
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.63
_cell_measurement_theta_min      2.33
_cell_volume                     19707(5)
_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)'
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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  0.0975
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            113907
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        24.897
_diffrn_reflns_theta_max         24.897
_diffrn_reflns_theta_min         1.226
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.082
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       block
_exptl_crystal_F_000             7872
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.243
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.585
_refine_diff_density_min         -0.241
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1217
_refine_ls_number_reflns         16865
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1303
_refine_ls_R_factor_gt           0.0688
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1156P)^2^+28.4866P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1778
_refine_ls_wR_factor_ref         0.2284
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8801
_reflns_number_total             16865
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00022_si_002.cif
_cod_data_source_block           tgh10039
_cod_depositor_comments
'Adding full bibliography for 4038084--4038097.cif.'
_cod_database_code               4038095
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.972
_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:
 C11(H11), C12(H12), C15(H15), C18(H18), C19(H19), C21(H21), C22(H22),
 C38(H38), C40(H40), C44(H44), C46(H46), C47(H47), C48(H48), C62(H62), C65(H65),
  C67(H67), C71(H71), C72(H72), C74(H74), C75(H75), C91(H91), C95(H95),
 C97(H97), C101(H101), C102(H102), C104(H104), C105(H105), C7AA(H7AA)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C20(H20A,H20B), C23(H23A,H23B), C37(H37A,H37B), C45(H45A,
 H45B), C49(H49A,H49B), C64(H64A,H64B), C73(H73A,H73B), C81(H81A,H81B),
 C94(H94A,H94B), C103(H10C,H10D), C107(H10E,H10F)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C27(H27), C28(H28), C29(H29),
 C30(H30), C31(H31), C41(H41), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57),
  C68(H68), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C98(H98),
 C0AA(H0AA)
2.d X=CH2 refined with riding coordinates:
 C10(H10A,H10B), C42(H42A,H42B), C69(H69A,H69B), C99(H99A,H99B)
2.e Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C),
 C26(H26A,H26B,H26C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C39(H39A,H39B,
 H39C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C59(H59A,H59B,H59C), C61(H61A,
 H61B,H61C), C66(H66A,H66B,H66C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C),
 C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C96(H96A,H96B,H96C), C108(H10G,H10H,
 H10I), C110(H11A,H11B,H11C)
2.f Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O2(H2A), O5(H5A), O6(H6), O9(H9), O10(H10), O13(H13), O14(H14)
;
_shelx_res_checksum              50732
_shelx_hkl_checksum              27254
_olex2_submission_special_instructions 'No special instructions were received'