Asymmetric Total Synthesis of Pre-schisanartanin C.
Jiang, Yan-Long; Yu, Hai-Xin; Li, Yong; Qu, Pei; Han, Yi-Xin; Chen, Jia-Hua; Yang, Zhen; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b11872

data_4133801
_publ_section_title
;
 Asymmetric Total Synthesis of Pre-schisanartanin C.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11872
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C44 H58 F2 O7 Si'
_chemical_formula_sum            'C44 H58 F2 O7 Si'
_chemical_formula_weight         764.99
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-22
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.07.11 svn.r3635 for OlexSys, GUI svn.r5848)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.44180(10)
_cell_length_b                   14.44180(10)
_cell_length_c                   40.0130(8)
_cell_measurement_reflns_used    17990
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      26.3920
_cell_measurement_theta_min      2.0050
_cell_volume                     8345.33(19)
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      180.00(10)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            57092
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         1.739
_exptl_absorpt_coefficient_mu    0.113
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65657
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             3280
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 2357 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     687
_refine_ls_number_reflns         9568
_refine_ls_number_restraints     560
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0675
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1048P)^2^+2.3213P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1790
_refine_ls_wR_factor_ref         0.1928
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                7232
_reflns_number_total             9568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11872_si_003.cif
_cod_data_source_block           3
_cod_original_cell_volume        8345.3(2)
_cod_database_code               4133801
_shelx_shelxl_version_number     2018/3
_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. Restrained distances
 C67-C4 = C77-C44
 1.54 with sigma of 0.02
 C48-C16 = C71-C78
 1.54 with sigma of 0.02
 C163-C159 = C108-C133 = C164-C138 = C159-C108 = C133-C164 = C138-C163 = C132-
 C20 = C32-C37 = C18-C27 = C20-C32 = C37-C18 = C27-C132
 1.4 with sigma of 0.01
 C112-C115 \\sim C161-C118
 with sigma of 0.02
 C130-C112 \\sim C161-C130
 with sigma of 0.02
 O127-C128 \\sim O145-C139
 with sigma of 0.02
 O145-C158 \\sim O127-C19
 with sigma of 0.02
 C19-C128 \\sim C139-C158
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C4 \\sim C67 \\sim C44 \\sim C77 \\sim C2 \\sim C62 \\sim C9 \\sim C39 \\sim
C16 \\sim C71 \\sim C48 \\sim C78 \\sim C66 \\sim C88 \\sim C101 \\sim C68
\\sim Si93 \\sim Si13 \\sim O15 \\sim O29 \\sim O31 \\sim O7: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C153 \\sim C122: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C2 \\sim C62: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
C161 \\sim C118 \\sim C115 \\sim C112 \\sim C130 \\sim C128 \\sim C139 \\sim
O127 \\sim O145 \\sim C19 \\sim C158 \\sim C159 \\sim C108 \\sim C132 \\sim C20
\\sim C32 \\sim C37 \\sim C18 \\sim C164 \\sim C138 \\sim C27 \\sim C163 \\sim
C133 \\sim C138 \\sim F25: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
4. Same fragment restrains
{O127, C19, C27, C18, C37, C32, C20, C132} sigma for 1-2: 0.01, 1-3: 0.01
as in
{O145, C158, C159, C163, C138, C164, C133, C108}
5. Others
 Sof(H13C)=Sof(C118)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C161)=Sof(H161)=
 Sof(C139)=Sof(H13D)=Sof(H13E)=Sof(O145)=Sof(C158)=Sof(H15D)=Sof(H15E)=
 Sof(C159)=Sof(H159)=Sof(C163)=Sof(H163)=Sof(C138)=Sof(C164)=Sof(H164)=
 Sof(C133)=Sof(H133)=Sof(C108)=Sof(F25)=1-FVAR(1)
 Sof(H130)=Sof(C112)=Sof(H112)=Sof(C115)=Sof(H11D)=Sof(H11E)=Sof(H11F)=
 Sof(O127)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C27)=Sof(H27)=Sof(C18)=Sof(H18)=
 Sof(C37)=Sof(C32)=Sof(H32)=Sof(C20)=Sof(H20)=Sof(C132)=Sof(C128)=Sof(H12D)=
 Sof(H12E)=Sof(F33)=FVAR(1)
 Sof(O15)=Sof(O7)=Sof(Si13)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C88)=
 Sof(H88A)=Sof(H88B)=Sof(H88C)=Sof(C67)=Sof(C48)=1-FVAR(2)
 Sof(Si93)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C68)=Sof(H68A)=Sof(H68B)=
 Sof(H68C)=Sof(C77)=Sof(C78)=Sof(O29)=Sof(O31)=FVAR(2)
 Fixed Uiso: H92(0) H94(0)
6.a Ternary CH refined with riding coordinates:
 C92(H92), C94(H94), C99(H99), C161(H161), C112(H112)
6.b Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C57(H57A,H57B), C70(H70A,H70B), C59(H59A,H59B), C134(H13A,
 H13B), C139(H13D,H13E), C158(H15D,H15E), C19(H19A,H19B), C128(H12D,H12E)
6.c Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C),
 C101(H10A,H10B,H10C), C88(H88A,H88B,H88C), C44(H44A,H44B,H44C), C62(H62A,H62B,
 H62C), C39(H39A,H39B,H39C), C71(H71A,H71B,H71C), C66(H66A,H66B,H66C), C68(H68A,
 H68B,H68C), C118(H11A,H11B,H11C), C115(H11D,H11E,H11F)
6.d Aromatic/amide H refined with riding coordinates:
 C147(H147), C155(H155), C117(H117), C168(H168), C130(H13C), C130(H130),
 C159(H159), C163(H163), C164(H164), C133(H133), C27(H27), C18(H18), C32(H32),
 C20(H20)
6.e Fitted hexagon refined as free rotating group:
 C69(C147,C155,C110,C117,C168)
6.f Idealised Me refined as rotating group:
 C149(H14A,H14B,H14C), C153(H15A,H15B,H15C), C120(H12A,H12B,H12C)
6.g :
 C166(H166)
;
_shelx_res_checksum              15588
_shelx_hkl_checksum              40959
_olex2_submission_special_instructions 'No special instructions were received'