Collective Syntheses of Guaiane Sesquiterpenes: Stereoselective Syntheses of (+)-Dysodensiol F, (+)-10β,14-Dihydroxy-<i>allo</i>-aromadendrane, and (-)-Dendroside C Aglycon.
Kim, Hyun Su; Park, Hyunkyung; Lim, Juhee; Lim, Changjin; Kim, Taewoo; Lee, Seungbeom; Hur, Joonseong; Sim, Jaehoon; Choi, Hyun Jin; Suh, Young-Ger; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01907

data_4038894
_publ_section_title
;
 Collective Syntheses of Guaiane Sesquiterpenes: Stereoselective Syntheses
 of (+)-Dysodensiol F, (+)-10\b,14-Dihydroxy-<i>allo</i>-aromadendrane,
 and (-)-Dendroside C Aglycon.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01907
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C30 H50 O4 S Si2'
_chemical_formula_sum            'C30 H50 O4 S Si2'
_chemical_formula_weight         562.94
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.36080(10)
_cell_length_b                   16.92910(10)
_cell_length_c                   23.1401(2)
_cell_measurement_reflns_used    10224
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      76.4040
_cell_measurement_theta_min      3.2200
_cell_volume                     3275.27(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.44a (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -113.00 -13.00   1.00    1.00    --  -41.24 -57.00 -60.00  100
  2  \w     17.00 116.00   1.00    1.00    --   41.24  38.00-180.00   99
  3  \w      1.00  82.00   1.00    1.00    --   41.24 -99.00 150.00   81
  4  \w     36.00 116.00   1.00    3.50    --  112.00-111.00 -30.00   80
  5  \w     59.00 178.00   1.00    3.50    --  112.00  15.00   0.00  119
  6  \w     36.00 116.00   1.00    3.50    --  112.00-111.00-150.00   80
  7  \w     36.00 116.00   1.00    3.50    --  112.00-111.00   0.00   80
  8  \w     39.00 138.00   1.00    3.50    --  112.00 -45.00 -30.00   99
  9  \w     36.00 116.00   1.00    3.50    --  112.00-111.00 -90.00   80
 10  \w     37.00  62.00   1.00    3.50    --  112.00-118.00  63.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1735805000
_diffrn_orient_matrix_UB_12      0.0174505000
_diffrn_orient_matrix_UB_13      -0.0183352000
_diffrn_orient_matrix_UB_21      -0.0443356000
_diffrn_orient_matrix_UB_22      0.0171627000
_diffrn_orient_matrix_UB_23      0.0634831000
_diffrn_orient_matrix_UB_31      0.0430841000
_diffrn_orient_matrix_UB_32      0.0876051000
_diffrn_orient_matrix_UB_33      0.0087417000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            16087
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.583
_diffrn_reflns_theta_min         3.235
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.814
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82174
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.44a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.142
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2831 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     376
_refine_ls_number_reflns         6834
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0276
_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^)+(0.0433P)^2^+0.6369P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0730
_reflns_Friedel_coverage         0.768
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                6623
_reflns_number_total             6834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01907_si_002.cif
_cod_data_source_block           exp_523
_cod_database_code               4038894
_chemical_oxdiff_formula         C30H50O4S1Si2
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C0AA) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C1AA) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
3. Others
 Sof(C0AB)=Sof(H0AD)=Sof(H0AE)=Sof(H0AF)=Sof(C1AB)=Sof(H1AE)=Sof(H1AF)=
 Sof(H1AG)=Sof(C2AA)=Sof(H2AB)=Sof(H2AC)=Sof(H2AD)=1-FVAR(1)
 Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=Sof(C00Y)=Sof(H3AA)=Sof(HH)=Sof(HI)=
 Sof(C1AA)=Sof(H1AB)=Sof(H1AC)=Sof(H1AD)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C00G(H00I), C00H(H00J), C00I(H00K), C009(H009)
4.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B), C00C(H00D,H00E), C00F(H00G,H00H)
4.c Aromatic/amide H refined with riding coordinates:
 C00B(H00C), C00E(H00F), C00P(H00Q), C00Q(H00R), C00R(H00S)
4.d X=CH2 refined with riding coordinates:
 C00J(H00L,H00M)
4.e Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C0AB(H0AD,H0AE,H0AF), C00L(H00N,H00O,H00P), C00S(H00T,
 H00U,H00V), C00T(H00W,H00X,H00Y), C00U(H00Z,H,HA), C00V(H00,HB,HC), C00W(H1AA,
 HD,HE), C00X(H2AA,HF,HG), C00Y(H3AA,HH,HI), C00Z(H4AA,HJ,HK), C1AA(H1AB,H1AC,
 H1AD), C1AB(H1AE,H1AF,H1AG), C2AA(H2AB,H2AC,H2AD)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-10-19
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.500
_oxdiff_exptl_absorpt_empirical_full_min 0.569