Total synthesis of (±)-tanshinol B, tanshinone I, and (±)-tanshindiol B and C.
Wang, Fan; Yang, Hong; Yu, Shujuan; Xue, Yu; Fan, Zhoulong; Liang, Gaolin; Geng, Meiyu; Zhang, Ao; Ding, Chunyong; Organic & biomolecular chemistry 16 (2018) 3376–3381; doi:10.1039/c8ob00567b

data_7157206
_publ_section_title
;
 Total synthesis of (+-)-tanshinol B, tanshinone I, and (+-)-tanshindiol B
 and C.
;
_journal_issue                   18
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3376
_journal_page_last               3381
_journal_paper_doi               10.1039/c8ob00567b
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C18 H16 O5, H2 O'
_chemical_formula_sum            'C18 H18 O6'
_chemical_formula_weight         330.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-26 deposited with the CCDC.
2018-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.828(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.373(2)
_cell_length_b                   9.0977(8)
_cell_length_c                   6.6706(6)
_cell_measurement_reflns_used    3272
_cell_measurement_temperature    205
_cell_measurement_theta_max      69.83
_cell_measurement_theta_min      3.68
_cell_volume                     1457.4(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      205
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            11941
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.122
_diffrn_reflns_theta_min         3.681
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.948
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.6062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1239 before and 0.0566 after correction. The Ratio of minimum to maximum transmission is 0.8043. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.148
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 835 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(10)
_refine_ls_extinction_coef       0.0012(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.973
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         2422
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.972
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0510P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0716
_refine_ls_wR_factor_ref         0.0735
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    0.812
_reflns_Friedel_fraction_max     0.810
_reflns_number_gt                2223
_reflns_number_total             2422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00567b2.cif
_cod_data_source_block           cu_2017935_0m
_cod_database_code               7157206
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.771
_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
 O6-H6B = O6-H6A
 0.84 with sigma of 0.02
3.a Free rotating group:
 O6(H6A)
3.b Ternary CH refined with riding coordinates:
 C10(H10)
3.c Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C11(H11A,H11B)
3.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C6(H6), C3(H3)
3.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C1(H1A,H1B,H1C)
3.f Idealised tetrahedral OH refined as rotating group:
 O4(H4), O5(H5)
;
_olex2_submission_special_instructions 'No special instructions were received'