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_4134751
_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         'C36 H66 O3 Si3'
_chemical_formula_sum            'C36 H66 O3 Si3'
_chemical_formula_weight         631.15
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.481(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.6743(7)
_cell_length_b                   10.7666(3)
_cell_length_c                   14.6325(4)
_cell_measurement_reflns_used    9470
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      29.5100
_cell_measurement_theta_min      2.4180
_cell_volume                     3822.39(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.907
_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     -9.00  17.00   0.50    1.00    --  -15.70 -57.00  90.00   52
  2  \w    -39.00 -12.00   0.50    1.00    --  -15.70  77.00  60.00   54
  3  \w    -34.00  -9.00   0.50    1.00    --  -15.70  77.00-120.00   50
  4  \w    -54.00 -28.00   0.50    1.00    --  -15.70  77.00 150.00   52
  5  \w    -54.00  -9.00   0.50    1.00    --  -15.70  77.00 -90.00   90
  6  \w    -57.00 -32.00   0.50    1.00    --  -15.70  77.00  90.00   50
  7  \w    -95.00 -32.00   0.50    1.00    --  -15.70 -57.00  90.00  126
  8  \w     42.00 105.00   0.50    1.00    --   15.80  19.00 -60.00  126
  9  \w    -39.00  25.00   0.50    1.00    --   15.80  19.00 -60.00  128
;
_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      0.0225397000
_diffrn_orient_matrix_UB_12      0.0340797000
_diffrn_orient_matrix_UB_13      0.0248912000
_diffrn_orient_matrix_UB_21      0.0164239000
_diffrn_orient_matrix_UB_22      -0.0545088000
_diffrn_orient_matrix_UB_23      0.0043632000
_diffrn_orient_matrix_UB_31      0.0087620000
_diffrn_orient_matrix_UB_32      0.0144350000
_diffrn_orient_matrix_UB_33      -0.0423233000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0292
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.907
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.502
_diffrn_reflns_theta_min         2.420
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.155
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49047
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
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    1.097
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     468
_refine_ls_number_reflns         9666
_refine_ls_number_restraints     265
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0443
_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^)+(0.0630P)^2^+0.5952P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1153
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7347
_reflns_number_total             9666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02522_si_006.cif
_cod_data_source_block           exp_3859
_cod_database_code               4134751
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.941
_reflns_odcompleteness_completeness 99.88
_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. Uiso/Uaniso restraints and constraints
O29 \\sim O117 \\sim Si78 \\sim Si54 \\sim C84 \\sim C11 \\sim C52 \\sim C22
\\sim C19 \\sim C36 \\sim C42 \\sim C23 \\sim C25 \\sim C30 \\sim C37 \\sim C53
\\sim C1: within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{O117, Si78, C37, C30, C1, C25, C23, C53} sigma for 1-2: 0.02, 1-3: 0.02
as
{O29, Si54, C36, C11, C22, C52, C42, C19}
4. Others
 Sof(O29)=Sof(Si54)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C11)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C52)=Sof(H52A)=
 Sof(H52B)=Sof(H52C)=Sof(C42)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(1)
 Sof(Si78)=Sof(O117)=Sof(C23)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C30)=
 Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C77(H77), C79(H79), C84(H84)
5.b Secondary CH2 refined with riding coordinates:
 C124(H12A,H12B), C93(H93A,H93B), C86(H86A,H86B), C88(H88A,H88B), C122(H12C,
 H12D), C106(H10A,H10B), C101(H10C,H10D), C105(H10E,H10F), C97(H97A,H97B),
 C58(H58B,H58A)
5.c Me refined with riding coordinates:
 C36(H36A,H36B,H36C), C11(H11D,H11E,H11F), C52(H52A,H52B,H52C)
5.d Me refined as rotating group:
 C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C25(H25A,H25B,H25C), C30(H30A,H30B,
 H30C), C37(H37A,H37B,H37C), C53(H53A,H53B,H53C), C1(H1A,H1B,H1C)
5.e Aromatic/amide H refined with riding coordinates:
 C89(H89)
5.f Idealised Me refined as rotating group:
 C112(H11C,H11A,H11B), C107(H10G,H10H,H10I), C130(H13A,H13B,H13C), C71(H71A,
 H71B,H71C), C61(H61C,H61A,H61B), C62(H62A,H62B,H62C), C43(H43A,H43B,H43C),
 C24(H24B,H24A,H24C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              18432
_shelx_hkl_checksum              76542
_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 1.545
_oxdiff_exptl_absorpt_empirical_full_min 0.643