Asymmetric Total Synthesis of (-)-Spirochensilide A.
Liang, Xin-Ting; Chen, Jia-Hua; Yang, Zhen; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02522

data_4134753
_publ_section_title
;
 Asymmetric Total Synthesis of (-)-Spirochensilide A.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02522
_journal_year                    2020
_chemical_formula_moiety         '2(C16.5 H29 O1.5 Si)'
_chemical_formula_sum            'C33 H58 O3 Si2'
_chemical_formula_weight         558.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-30
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                93.828(5)
_cell_angle_beta                 96.178(5)
_cell_angle_gamma                92.265(5)
_cell_formula_units_Z            4
_cell_length_a                   7.3602(5)
_cell_length_b                   17.1118(11)
_cell_length_c                   26.8552(16)
_cell_measurement_reflns_used    1937
_cell_measurement_temperature    106.4
_cell_measurement_theta_max      29.2950
_cell_measurement_theta_min      2.9644
_cell_volume                     3351.4(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      106.4
_diffrn_detector_area_resol_mean 16.0971
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega   -5.00   26.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.8148 -118.0000  -43.0000 31

  2 omega  -63.00  -33.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.8148  -37.0000   60.0000 30

  3 omega  -86.00  -54.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.8148  -37.0000  120.0000 32

  4 omega   24.00   49.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711  -77.0000  -30.0000 25

  5 omega  -30.00   -2.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711  -77.0000  -30.0000 28

  6 omega   25.00   88.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711   37.0000 -150.0000 63

  7 omega    5.00   88.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711   37.0000    0.0000 83

  8 omega   -5.00   72.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711 -118.0000  137.0000 77

  9 omega   27.00   78.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711   77.0000   30.0000 51

 10 omega   -5.00   76.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9711   37.0000  -60.0000 81
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0209713000
_diffrn_orient_matrix_UB_12      -0.0000826000
_diffrn_orient_matrix_UB_13      0.0264009000
_diffrn_orient_matrix_UB_21      -0.0496102000
_diffrn_orient_matrix_UB_22      -0.0364506000
_diffrn_orient_matrix_UB_23      -0.0003060000
_diffrn_orient_matrix_UB_31      0.0807207000
_diffrn_orient_matrix_UB_32      -0.0200263000
_diffrn_orient_matrix_UB_33      -0.0035062000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1153
_diffrn_reflns_av_unetI/netI     0.1969
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            29719
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         2.970
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.135
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.108
_exptl_crystal_description       needle
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.309
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     849
_refine_ls_number_reflns         13168
_refine_ls_number_restraints     167
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.1769
_refine_ls_R_factor_gt           0.0824
_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^)+(0.0200P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1470
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6584
_reflns_number_total             13168
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02522_si_003.cif
_cod_data_source_block           xprep
_cod_database_code               4134753
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.948
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
Si3B \\sim Si3A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
3. Rigid body (RIGU) restrains
 C1BA, C2BA, C4, C2BB, C6BA, C1BB, C7, C3BA, C4BA, C5BA, C3BB, C5BB, C4BB,
 C7BA, Si0A, Si0B, Si3B, Si3A, C1BA, C2BA, C7AA, C4, C2BB, C4A, C6BA, C1BB,
 Si3B, O4, C1, C2, C1A, C2A, Si3A, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C7)=Sof(Si0B)=Sof(C3A)=Sof(H3AD)=Sof(H3AE)=Sof(H3AF)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(H8AC)=Sof(C3BB)=Sof(H3BD)=Sof(H3BE)=Sof(H3BF)=Sof(C5BB)=
 Sof(H5BD)=Sof(H5BE)=Sof(H5BF)=Sof(C4BB)=Sof(H4BD)=Sof(H4BE)=Sof(H4BF)=1-FVAR(1)
 Sof(Si0A)=Sof(C3BA)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=Sof(C4BA)=Sof(H4BA)=
 Sof(H4BB)=Sof(H4BC)=Sof(C5BA)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C7BA)=FVAR(1)
 Sof(C1A)=Sof(H1AD)=Sof(H1AE)=Sof(H1AF)=Sof(C2A)=Sof(H2AD)=Sof(H2AE)=Sof(H2AF)=
 Sof(C2BB)=Sof(C4A)=Sof(H4AD)=Sof(H4AE)=Sof(H4AF)=Sof(C6BA)=Sof(H6BA)=Sof(H6BB)=
 Sof(H6BC)=Sof(C1BB)=Sof(H1BD)=Sof(H1BE)=Sof(H1BF)=Sof(Si3A)=1-FVAR(2)
 Sof(Si3B)=Sof(C1BA)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C2BA)=Sof(C1)=Sof(H1A)=
 Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C7AA)=Sof(H7AA)=
 Sof(H7AB)=Sof(H7AC)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C18(H18), C29(H29), C38(H38)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C22(H22A,H22B), C24(H24A,H24B), C26(H26A,H26B), C31(H31A,
 H31B), C33(H33A,H33B), C34(H34A,H34B), C36(H36A,H36B), C39(H39A,H39B),
 C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B),
  C49(H49A,H49B), C51(H51A,H51B)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C43(H43A,H43B,H43C), C0AA(H0AA,H0AB,H0AC),
 C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,H2AC), C3AA(H3AA,H3AB,H3AC), C4AA(H4AA,
 H4AB,H4AC), C5AA(H5AA,H5AB,H5AC), C6AA(H6AA,H6AB,H6AC), C8AA(H8AD,H8AE,H8AF),
 C9AA(H9AA,H9AB,H9AC), C0BA(H0BA,H0BB,H0BC), C1BA(H1BA,H1BB,H1BC), C3BA(H3BA,
 H3BB,H3BC), C4BA(H4BA,H4BB,H4BC), C5BA(H5BA,H5BB,H5BC), C3(H3A,H3B,H3C),
 C8(H8A,H8B,H8C), C3A(H3AD,H3AE,H3AF), C8A(H8AA,H8AB,H8AC), C3BB(H3BD,H3BE,
 H3BF), C5BB(H5BD,H5BE,H5BF), C4BB(H4BD,H4BE,H4BF), C1(H1A,H1B,H1C), C2(H2A,H2B,
 H2C), C7AA(H7AA,H7AB,H7AC), C4(H4A,H4B,H4C), C1A(H1AD,H1AE,H1AF), C2A(H2AD,
 H2AE,H2AF), C4A(H4AD,H4AE,H4AF), C6BA(H6BA,H6BB,H6BC), C1BB(H1BD,H1BE,H1BF)
;
_shelx_res_checksum              49478
_shelx_hkl_checksum              1049
_olex2_submission_special_instructions 'No special instructions were received'