An Iminium Ion Cascade Annulation Strategy for the Synthesis of Akuammiline Alkaloid Pentacyclic Core Structures.
Andreansky, Eric S.; Blakey, Simon B.; Organic letters 18 (2016) 6492–6495; doi:10.1021/acs.orglett.6b03406

data_1555990
_publ_section_title
;
 An Iminium Ion Cascade Annulation Strategy for the Synthesis of
 Akuammiline Alkaloid Pentacyclic Core Structures.
;
_journal_issue                   24
_journal_name_full               'Organic letters'
_journal_page_first              6492
_journal_page_last               6495
_journal_paper_doi               10.1021/acs.orglett.6b03406
_journal_volume                  18
_journal_year                    2016
_chemical_formula_moiety         'C47 H50 N2 O5 S Si'
_chemical_formula_sum            'C47 H50 N2 O5 S Si'
_chemical_formula_weight         783.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-09-09
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.08.21 svn.r2771 for OlexSys, GUI svn.r4586)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.4057(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.0823(17)
_cell_length_b                   18.0956(19)
_cell_length_c                   28.619(3)
_cell_measurement_reflns_used    9408
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      30.391
_cell_measurement_theta_min      2.362
_cell_volume                     8259.2(15)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
'O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341.'
_computing_publication_material
'O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341.'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  profile_Bruker_APEX2_Mo
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            36451
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         1.702
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.156
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0672 before and 0.0525 after correction.
The Ratio of minimum to maximum transmission is 0.8393.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_description       prism
_exptl_crystal_F_000             3328
_exptl_crystal_size_max          0.797
_exptl_crystal_size_mid          0.483
_exptl_crystal_size_min          0.355
_refine_diff_density_max         0.493
_refine_diff_density_min         -0.384
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.155
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         9120
_refine_ls_number_restraints     318
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0941
_refine_ls_R_factor_gt           0.0684
_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^)+(0.0301P)^2^+26.9778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1326
_refine_ls_wR_factor_ref         0.1526
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6979
_reflns_number_total             9120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b03406_si_002.cif
_cod_data_source_block           esa9613
_cod_database_code               1555990
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.885
_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
 C16-H16B = C16-H16A
 0.995 with sigma of 0.005
 Si1-C33B \\sim Si1-C33A
 with sigma of 0.005
 Si1-C37 \\sim Si1-C37'
 with sigma of 0.005
 C19B-C18 \\sim C19A-C18
 with sigma of 0.005
3. Restrained planarity
 C37, C38, C42, C39, C41, C40
 with sigma of 0.005
 C24A, C19A, C20A, C21A, C23A, C22A
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
C39' \\sim C39 \\sim C37 \\sim C38 \\sim H38 \\sim H39 \\sim C40 \\sim H40
\\sim C41 \\sim H41 \\sim C42 \\sim H42 \\sim C37' \\sim C38' \\sim H38' \\sim
H39' \\sim C40' \\sim H40' \\sim C41' \\sim C42' \\sim H42': within 1.2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C33A) = Uanis(C33B)
Uanis(C34A) = Uanis(C34B)
Uanis(C36A) = Uanis(C36B)
Uanis(C35A) = Uanis(C35B)
Uanis(C19A) = Uanis(C19B)
Uanis(C20A) = Uanis(C20B)
Uanis(C21A) = Uanis(C21B)
Uanis(C22A) = Uanis(C22B)
Uanis(C23A) = Uanis(C23B)
Uanis(C24A) = Uanis(C24B)
Uanis(C37) = Uanis(C37')
5. Rigid body (RIGU) restrains
 C33A, C34A, C35A, C36A, C33B, C34B, C35B, C36B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19A, C20A, C21A, C22A, C23A, C24A, C19B, C20B, C21B, C22B, C23B, C24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, C38, C39, C40, C41, C42, C37', C38', C39', C40', C41', C42'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{C19B, C20B, C21B, C22B, C23B, C24B}
as
{C19A, C20A, C21A, C22A, C23A, C24A}
{C33B, C34B, C35B, C36B}
as
{C33A, C34A, C35A, C36A}
7. Others
 Sof(C33B)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35B)=Sof(H35D)=
 Sof(H35E)=Sof(H35F)=Sof(C36B)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C33A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35A)=Sof(H35A)=
 Sof(H35B)=Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
 Sof(C37')=Sof(C38')=Sof(H38')=Sof(C39')=Sof(H39')=Sof(C40')=Sof(H40')=
 Sof(C41')=Sof(H41')=Sof(C42')=Sof(H42')=1-FVAR(2)
 Sof(C37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=Sof(C41)=
 Sof(H41)=Sof(C42)=Sof(H42)=FVAR(2)
 Sof(C19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(C22B)=Sof(H22B)=
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=1-FVAR(3)
 Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C7(H7)
8.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C4(H4A,H4B), C5(H5A,H5B), C9(H9A,H9B), C32(H32A,H32B)
8.c Aromatic/amide H refined with riding coordinates:
 C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C20B(H20B),
 C21B(H21B), C22B(H22B), C23B(H23B), C24B(H24B), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42), C38'(H38'), C39'(H39'), C40'(H40'), C41'(H41'), C42'(H42'),
  C11(H11), C12(H12), C13(H13), C14(H14), C26(H26), C27(H27), C29(H29),
 C30(H30), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48)
8.d Idealised Me refined as rotating group:
 C34A(H34A,H34B,H34C), C35A(H35A,H35B,H35C), C36A(H36A,H36B,H36C), C34B(H34D,
 H34E,H34F), C35B(H35D,H35E,H35F), C36B(H36D,H36E,H36F), C31(H31A,H31B,H31C)
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