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_4134755
_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         'C53 H86 Br2 O6 Si3'
_chemical_formula_sum            'C53 H86 Br2 O6 Si3'
_chemical_formula_weight         1063.30
_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             2019-09-03
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_cell_angle_alpha                73.227(2)
_cell_angle_beta                 81.077(2)
_cell_angle_gamma                71.980(2)
_cell_formula_units_Z            2
_cell_length_a                   11.6286(3)
_cell_length_b                   15.8231(4)
_cell_length_c                   17.4203(5)
_cell_measurement_reflns_used    13667
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      27.1230
_cell_measurement_theta_min      2.1540
_cell_volume                     2910.80(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.29a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29a (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.903
_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    -52.00 -18.00   0.50    4.00    --  -15.70  77.00 -30.00   68
  2  \w    -40.00 -12.00   0.50    4.00    --  -15.70  77.00-150.00   56
  3  \w    -57.00 -26.00   0.50    4.00    --  -15.70  77.00  60.00   62
  4  \w    -57.00  51.00   0.50    4.00    --  -15.70 -37.00-150.00  216
  5  \w    -56.00 -23.00   0.50    4.00    --  -15.70  77.00 150.00   66
  6  \w    -15.00  30.00   0.50    4.00    --  -15.70 -82.00 150.00   90
  7  \w    -26.00  27.00   0.50    4.00    --   15.80 -82.00-180.00  106
  8  \w    -35.00  52.00   0.50    4.00    --   15.80 -77.00  30.00  174
  9  \w     62.00  98.00   0.50    4.00    --   15.80 -19.00 120.00   72
 10  \w    -69.00   8.00   0.50    4.00    --   15.80 -19.00 120.00  154
 11  \w    -69.00  49.00   0.50    4.00    --   15.80 -57.00  60.00  236
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0152202000
_diffrn_orient_matrix_UB_12      0.0427953000
_diffrn_orient_matrix_UB_13      -0.0291593000
_diffrn_orient_matrix_UB_21      -0.0312868000
_diffrn_orient_matrix_UB_22      0.0218052000
_diffrn_orient_matrix_UB_23      0.0305609000
_diffrn_orient_matrix_UB_31      0.0540864000
_diffrn_orient_matrix_UB_32      0.0084363000
_diffrn_orient_matrix_UB_33      0.0058072000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.903
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            41359
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.479
_diffrn_reflns_theta_min         2.140
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.497
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54671
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.919
_refine_diff_density_min         -0.672
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     637
_refine_ls_number_reflns         14604
_refine_ls_number_restraints     315
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0500
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0487P)^2^+1.3198P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1066
_refine_ls_wR_factor_ref         0.1187
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9855
_reflns_number_total             14604
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02522_si_007.cif
_cod_data_source_block           exp_4397
_cod_database_code               4134755
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.586
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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. Shared sites
{C61, C150}
3. Rigid bond restraints
 Si32, C55
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C97, C150
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 Si40, C17
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C115, C155
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 Si52, C115
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C61 \\sim C85 \\sim C97 \\sim C168 \\sim C150 \\sim C152 \\sim C6 \\sim C53
\\sim Si32 \\sim Si16: within 2.5A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2.5A
Uanis(C1) \\sim Ueq, Uanis(C158) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C99) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.005
Uanis(C61) = Uanis(C150)
5. Rigid body (RIGU) restrains
 Si32, C55, C61, C85, C151, C71, C97, C168, Si16, C150, C152, C158, C1, C6, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C61)=Sof(Si16)=Sof(C152)=Sof(H15J)=Sof(H15K)=Sof(H15L)=Sof(C158)=
 Sof(H15M)=Sof(H15N)=Sof(H15O)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C6)=
 Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=1-FVAR(1)
 Sof(Si32)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=Sof(C151)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C97)=Sof(H97A)=
 Sof(H97B)=Sof(H97C)=Sof(C168)=Sof(H16I)=Sof(H16J)=Sof(H16K)=Sof(C150)=FVAR(1)
7.a Free rotating group:
 Si16(C150,C152,C158,C1,C6,C53)
7.b Ternary CH refined with riding coordinates:
 C106(H106), C112(H112), C136(H136), C76(H76), C46(H46), C120(H120)
7.c Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C16(H16A,H16B), C110(H11A,H11B), C78(H78A,H78B), C124(H12A,
 H12B), C96(H96A,H96B), C142(H14A,H14B), C57(H57A,H57B), C127(H12F,H12G),
 C17(H17A,H17B), C65(H65A,H65B)
7.d Aromatic/amide H refined with riding coordinates:
 C118(H118), C94(H94), C144(H144), C2(H2)
7.e Idealised Me refined with riding coordinates:
 C85(H85A,H85B,H85C), C97(H97A,H97B,H97C), C168(H16I,H16J,H16K), C152(H15J,
 H15K,H15L), C6(H6A,H6B,H6C), C53(H53A,H53B,H53C)
7.f Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C128(H12C,H12D,H12E), C137(H13A,H13B,H13C), C69(H69A,
 H69B,H69C), C125(H12H,H12I,H12J), C165(H16C,H16D,H16E), C151(H15A,H15B,H15C),
 C79(H79A,H79B,H79C), C71(H71A,H71B,H71C), C155(H15D,H15E,H15F), C161(H16F,H16G,
 H16H), C145(H14C,H14D,H14E), C156(H15G,H15H,H15I), C171(H17C,H17D,H17E),
 C99(H99A,H99B,H99C), C158(H15M,H15N,H15O), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              8194
_shelx_hkl_checksum              36213
_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 2.491
_oxdiff_exptl_absorpt_empirical_full_min 0.500