Convergent Route to ent-Kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α,6α-Diacetoxy-ent-kaura-9(11),16-dien-12,15-dione.
Zhao, Xiangbo; Li, Wu; Wang, Junjie; Ma, Dawei; Journal of the American Chemical Society 139 (2017) 2932–2935; doi:10.1021/jacs.7b00140

data_4125661
_publ_section_title
;
 Convergent Route to ent-Kaurane Diterpenoids: Total Synthesis of
 Lungshengenin D and
 1\a,6\a-Diacetoxy-ent-kaura-9(11),16-dien-12,15-dione.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2932
_journal_page_last               2935
_journal_paper_doi               10.1021/jacs.7b00140
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C22 H34 O4'
_chemical_formula_sum            'C22 H34 O4'
_chemical_formula_weight         362.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.29(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.229(16)
_cell_length_b                   6.209(9)
_cell_length_c                   14.14(2)
_cell_measurement_reflns_used    351
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      17.079
_cell_measurement_theta_min      2.971
_cell_volume                     906(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_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 (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.894
_diffrn_measured_fraction_theta_max 0.968
_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  0.1492
_diffrn_reflns_av_unetI/netI     0.2833
_diffrn_reflns_Laue_measured_fraction_full 0.894
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5739
_diffrn_reflns_point_group_measured_fraction_full 0.846
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.247
_diffrn_reflns_theta_min         1.975
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.3536
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1145 before and 0.0742 after correction.
The Ratio of minimum to maximum transmission is 0.4743.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       needle
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 241 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   2.5(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.953
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         3004
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.2564
_refine_ls_R_factor_gt           0.0959
_refine_ls_shift/su_max          0.028
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0857P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1869
_refine_ls_wR_factor_ref         0.2626
_reflns_Friedel_coverage         0.721
_reflns_Friedel_fraction_full    0.787
_reflns_Friedel_fraction_max     0.855
_reflns_number_gt                1078
_reflns_number_total             3004
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00140_si_005.cif
_cod_data_source_block           mo_dm15593_0m
_cod_original_cell_volume        905(2)
_cod_database_code               4125661
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.982
_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. Uiso/Uaniso restraints and constraints
O3 \\sim O4 \\sim C18 \\sim C19: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C1(H1A), C5(H5), C6(H6), C9(H9), C13(H13)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B), C11(H11A,H11B), C15(H15A,H15B),
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
3.c X=CH2 refined with riding coordinates:
 C16(H16A,H16B)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_shelx_res_checksum              10618
_shelx_hkl_checksum              81113
_olex2_submission_special_instructions 'No special instructions were received'