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_4134756
_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 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.318(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.3242(13)
_cell_length_b                   20.6520(16)
_cell_length_c                   19.7232(18)
_cell_measurement_reflns_used    4671
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      22.3790
_cell_measurement_theta_min      2.8760
_cell_volume                     7807.1(11)
_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 (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      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -32.00  31.00   0.50   37.00    --   -1.40 -82.00   0.00  126
  2  \w      3.00  84.00   0.50   37.00    --    1.60  19.00 120.00  162
  3  \w    -88.00  19.00   0.50   37.00    --    1.60 -37.00 -30.00  214
  4  \w    -82.00 -57.00   0.50   37.00    --    1.60 -37.00  60.00   50
  5  \w    -10.00  21.00   0.50   37.00    --    1.60 -37.00  60.00   62
  6  \w     26.00  54.00   0.50   37.00    --    1.60  19.00  90.00   56
  7  \w     26.00  51.00   0.50   37.00    --    1.60  37.00-180.00   50
;
_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      -0.0346980000
_diffrn_orient_matrix_UB_12      0.0115094000
_diffrn_orient_matrix_UB_13      -0.0073316000
_diffrn_orient_matrix_UB_21      -0.0101544000
_diffrn_orient_matrix_UB_22      -0.0196649000
_diffrn_orient_matrix_UB_23      0.0264924000
_diffrn_orient_matrix_UB_31      0.0078631000
_diffrn_orient_matrix_UB_32      0.0256729000
_diffrn_orient_matrix_UB_33      0.0236917000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1773
_diffrn_reflns_av_unetI/netI     0.1015
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            96966
_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         2.230
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.152
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47099
_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    1.074
_exptl_crystal_description       needle
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     945
_refine_ls_number_reflns         15364
_refine_ls_number_restraints     599
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1566
_refine_ls_R_factor_gt           0.0897
_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^)+(0.0734P)^2^+8.0955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1803
_refine_ls_wR_factor_ref         0.2124
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8869
_reflns_number_total             15364
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02522_si_005.cif
_cod_data_source_block           exp_3940
_cod_database_code               4134756
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O'
_reflns_odcompleteness_completeness 99.87
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C187-C63 \\sim C52-C69
 with sigma of 0.02
 C187-C55 \\sim C52-C61
 with sigma of 0.02
 C187-C66 \\sim C52-C49
 with sigma of 0.02
 C187-C96 \\sim C52-C36
 with sigma of 0.02
 C187-C65 \\sim C52-C40
 with sigma of 0.02
 C96-C65 \\sim C36-C40
 with sigma of 0.02
 C63-C55 \\sim C69-C61
 with sigma of 0.02
 C63-C66 \\sim C69-C49
 with sigma of 0.02
 C55-C66 \\sim C61-C49
 with sigma of 0.02
 Si13-C187 \\sim Si35-C52
 with sigma of 0.02
 Si13-C96 \\sim Si35-C36
 with sigma of 0.02
 Si13-C65 \\sim Si35-C40
 with sigma of 0.02
 Si13-C63 \\sim Si35-C69
 with sigma of 0.02
 Si13-C55 \\sim Si35-C61
 with sigma of 0.02
 Si13-C66 \\sim Si35-C49
 with sigma of 0.02
 Si13-O129 \\sim Si35-O129
 with sigma of 0.02
 O129-C187 \\sim O129-C52
 with sigma of 0.02
 O129-C96 \\sim O129-C36
 with sigma of 0.02
 O129-C65 \\sim O129-C40
 with sigma of 0.02
 C1-Si11 \\sim Si11-C1 \\sim C5-Si11 \\sim Si11-C1 \\sim C2-Si11 \\sim Si11-C6
 with sigma of 0.02
 C241-C86 \\sim C241-C86A
 with sigma of 0.02
 C241-C97 \\sim C241-C97A
 with sigma of 0.02
 C241-C73 \\sim C241-C73A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si13 \\sim C187 \\sim C96 \\sim C63 \\sim C55 \\sim C65 \\sim C66 \\sim C61
\\sim C52 \\sim C69 \\sim C49 \\sim Si35 \\sim C36 \\sim C40: within 2.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C254 \\sim C79 \\sim C1 \\sim C60 \\sim C20 \\sim C211 \\sim C4 \\sim Si16
\\sim C78 \\sim C28 \\sim C32 \\sim C255: within 2.5A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Si11 \\sim C1 \\sim C3 \\sim C54B \\sim C2 \\sim C93B \\sim C7 \\sim C254 \\sim
C79 \\sim C5 \\sim C54A \\sim C93A \\sim C6: within 2.5A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C73 \\sim C73A \\sim C241 \\sim C86 \\sim C86A \\sim C97 \\sim C97A: within
2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C97A) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C86A) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C73A) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of 0.05 and
sigma for terminal atoms of 0.05
4. Same fragment restrains
{C78, C4, C32} sigma for 1-2: 0.02, 1-3: 0.02
as
{C28, C255, C78}
{C5, C54A, C6, C93A, C1, C79} sigma for 1-2: 0.02, 1-3: 0.02
as
{C3, C54B, C2, C93B, C7, C254}
5. Others
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C52)=Sof(C69)=Sof(H69A)=Sof(H69B)=
 Sof(H69C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(Si35)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=1-FVAR(1)
 Sof(Si13)=Sof(C187)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C65)=Sof(H65A)=
 Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(1)
 Sof(H21H)=Sof(H21I)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=1-FVAR(2)
 Sof(H21F)=Sof(H21G)=Sof(C20)=Sof(H20K)=Sof(H20L)=Sof(H20M)=FVAR(2)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C255)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=1-FVAR(3)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 FVAR(3)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C93A)=Sof(H93D)=
 Sof(H93E)=Sof(H93F)=Sof(C6)=Sof(H6A)=Sof(H6B)=1-FVAR(4)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C54B)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C93B)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(C254)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(4)
 Sof(C97A)=Sof(H97D)=Sof(H97E)=Sof(H97F)=Sof(C73A)=Sof(H73D)=Sof(H73E)=
 Sof(H73F)=Sof(C86A)=Sof(H86D)=Sof(H86E)=Sof(H86F)=1-FVAR(5)
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C153(H153), C132(H132), C156(H156), C150(H150), C161(H161), C151(H151)
6.b Secondary CH2 refined with riding coordinates:
 C164(H16C,H16D), C159(H15A,H15B), C158(H15C,H15D), C145(H14A,H14B), C169(H16A,
 H16B), C128(H12A,H12B), C148(H14C,H14D), C119(H11A,H11B), C181(H18D,H18E),
 C246(H24A,H24B), C205(H20D,H20E), C201(H20F,H20G), C217(H21A,H21B), C192(H19A,
 H19B), C211(H21H,H21I), C211(H21F,H21G), C240(H24C,H24D), C1(H1A,H1B),
 C220(H22D,H22E), C3(H3A,H3B), C2(H2A,H2B), C7(H7A,H7B), C5(H5A,H5B), C6(H6A,
 H6B)
6.c Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C255(H25D,H25E,H25F), C78(H78A,H78B,H78C), C234(H23A,
 H23B,H23C), C54B(H54A,H54B,H54C), C93B(H93A,H93B,H93C), C254(H25A,H25B,H25C),
 C86(H86A,H86B,H86C), C96(H96A,H96B,H96C), C89(H89A,H89B,H89C), C97(H97A,H97B,
 H97C), C73(H73A,H73B,H73C), C79(H79A,H79B,H79C), C60(H60A,H60B,H60C), C63(H63A,
 H63B,H63C), C55(H55A,H55B,H55C), C65(H65A,H65B,H65C), C32(H32A,H32B,H32C),
 C66(H66A,H66B,H66C), C61(H61A,H61B,H61C), C69(H69A,H69B,H69C), C49(H49A,H49B,
 H49C), C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C20(H20K,H20L,H20M),
 C54A(H54D,H54E,H54F), C93A(H93D,H93E,H93F), C97A(H97D,H97E,H97F), C73A(H73D,
 H73E,H73F), C86A(H86D,H86E,H86F)
6.d Aromatic/amide H refined with riding coordinates:
 C172(H172), C212(H212)
6.e Idealised Me refined as rotating group:
 C222(H22A,H22B,H22C), C214(H21J,H21K,H21L), C183(H18A,H18B,H18C), C218(H21C,
 H21D,H21E), C242(H24E,H24F,H24G), C206(H20A,H20B,H20C), C207(H20H,H20I,H20J),
 C114(H11C,H11D,H11E), C100(H10A,H10B,H10C), C109(H10D,H10E,H10F), C98(H98A,
 H98B,H98C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              67469
_shelx_hkl_checksum              40533
_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 1.665
_oxdiff_exptl_absorpt_empirical_full_min 0.564