11-Step Total Synthesis of Araiosamines.
Tian, Maoqun; Yan, Ming; Baran, Phil S.; Journal of the American Chemical Society 138 (2016) 14234–14237; doi:10.1021/jacs.6b09701

data_4131126
_publ_section_title
;
 11-Step Total Synthesis of Araiosamines.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14234
_journal_page_last               14237
_journal_paper_doi               10.1021/jacs.6b09701
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C42 H46 Br3 N9 O3 Si'
_chemical_formula_sum            'C42 H46 Br3 N9 O3 Si'
_chemical_formula_weight         992.70
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-06-01
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                101.908(2)
_cell_angle_beta                 103.234(2)
_cell_angle_gamma                108.766(2)
_cell_formula_units_Z            12
_cell_length_a                   17.7258(8)
_cell_length_b                   26.2139(13)
_cell_length_c                   34.8331(17)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    100
_cell_measurement_theta_max      19.154
_cell_measurement_theta_min      2.353
_cell_volume                     14213.2(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 8.258
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1331
_diffrn_reflns_av_unetI/netI     0.1107
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            266000
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        23.326
_diffrn_reflns_theta_max         23.326
_diffrn_reflns_theta_min         1.233
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.625
_exptl_absorpt_correction_T_max  0.0886
_exptl_absorpt_correction_T_min  0.0622
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1315 before and 0.0676 after correction.
The Ratio of minimum to maximum transmission is 0.7020.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_colour_primary    Colorless
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       Block
_exptl_crystal_F_000             6048
_exptl_crystal_size_max          0.117
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.096
_refine_diff_density_max         1.740
_refine_diff_density_min         -1.125
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3378
_refine_ls_number_reflns         41053
_refine_ls_number_restraints     291
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.1425
_refine_ls_R_factor_gt           0.0703
_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^)+(0.0716P)^2^+40.0444P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22576
_reflns_number_total             41053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b09701_si_007.cif
_cod_data_source_block           Baran573
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/ACS/depositions/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4131126
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.749
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 O3E-C32E = O3EB-C32F
 1.3 with sigma of 0.02
 N6E-C32E = N6E-C32F
 1.35 with sigma of 0.02
 O3E-C33E = O3EB-C33F
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C39D) = Uanis(C39G)
Uanis(Si1F) = Uanis(Si1E)
Uanis(C37E) = Uanis(C38F)
Uanis(O3E) = Uanis(O3EB)
Uanis(C32F) = Uanis(C32E)
4. Rigid body (RIGU) restrains
 C41D, C39D, C40D, C42D
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N2D, N3DB, N4DB
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N2B, N3BD, N4BD
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Si1F, C37F, C39F, C40F, C41F, C42F
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O2E, O3E, O2EB, O3EB, N6E, C32E, C33E, C34E, C35E, C36E, C32F, C33F, C34F,
 C35F, C36F
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Si1E, Si1F, O1E, C37E, C38E, C39E, C40E, C41E, C42E, C37F, C38F, C39F, C40F,
 C41F, C42F
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N2E, N3E, N4E, N3EB, N4EB
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{Si1, C37, C38, C39, C40, C41, C42} sigma for 1-2: 0.02, 1-3: 0.04
as
{Si1F, C37F, C38F, C39F, C40F, C41F, C42F}
6. Others
 Sof(N3BD)=Sof(N4BD)=1-FVAR(1)
 Sof(N3B)=Sof(N4B)=FVAR(1)
 Sof(Si1G)=Sof(H37J)=Sof(H37K)=Sof(H37L)=Sof(H38J)=Sof(H38K)=Sof(H38L)=
 Sof(H41J)=Sof(H41K)=Sof(H41L)=Sof(C39G)=Sof(C40G)=Sof(H40J)=Sof(H40K)=
 Sof(H40L)=Sof(C42G)=Sof(H42J)=Sof(H42K)=Sof(H42L)=1-FVAR(2)
 Sof(Si1D)=Sof(H37G)=Sof(H37H)=Sof(H37I)=Sof(H38G)=Sof(H38H)=Sof(H38I)=
 Sof(H41G)=Sof(H41H)=Sof(H41I)=Sof(C39D)=Sof(C40D)=Sof(H40G)=Sof(H40H)=
 Sof(H40I)=Sof(C42D)=Sof(H42G)=Sof(H42H)=Sof(H42I)=FVAR(2)
 Sof(N3EB)=Sof(N4EB)=1-FVAR(3)
 Sof(N3E)=Sof(N4E)=FVAR(3)
 Sof(N3DB)=Sof(N4DB)=1-FVAR(4)
 Sof(N3D)=Sof(N4D)=FVAR(4)
 Sof(Si1F)=Sof(C37F)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38F)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=Sof(C39F)=Sof(C40F)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41F)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42F)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=1-FVAR(5)
 Sof(Si1E)=Sof(C37E)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38E)=Sof(H38D)=
 Sof(H38E)=Sof(H38F)=Sof(C39E)=Sof(C40E)=Sof(H40D)=Sof(H40E)=Sof(H40F)=
 Sof(C41E)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42E)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=FVAR(5)
 Fixed Sof: O2E(0.5) O3E(0.5) O2EB(0.5) O3EB(0.5) C32E(0.5) C33E(0.5)
 C34E(0.5) H34A(0.5) H34B(0.5) H34C(0.5) C35E(0.5) H35A(0.5) H35B(0.5)
 H35C(0.5) C36E(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C32F(0.5) C33F(0.5)
 C34F(0.5) H34D(0.5) H34E(0.5) H34F(0.5) C35F(0.5) H35D(0.5) H35E(0.5)
 H35F(0.5) C36F(0.5) H36D(0.5) H36E(0.5) H36F(0.5)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5A), C6(H6), C1A(H1A), C2A(H2A), C3A(H3A),
  C4A(H4A), C5A(H5AB), C6A(H6A), C1B(H1B), C2B(H2B), C3B(H3B), C4B(H4B),
 C5B(H5BA), C6B(H6B), C1C(H1C), C2C(H2C), C3C(H3C), C4C(H4C), C5C(H5CA),
 C6C(H6C), C1D(H1D), C2D(H2D), C3D(H3D), C4D(H4D), C5D(H5DA), C6D(H6D),
 C1E(H1E), C2E(H2E), C3E(H3E), C4E(H4E), C5E(H5EA), C6E(H6E)
7.b Me refined with riding coordinates:
 C37D(H37G,H37H,H37I), C37D(H37J,H37K,H37L), C38D(H38J,H38K,H38L), C38D(H38G,
 H38H,H38I), C41D(H41J,H41K,H41L), C41D(H41G,H41H,H41I), C42F(H42A,H42B,H42C)
7.c Aromatic/amide H refined with riding coordinates:
 N5(H5), N7(H7), N8(H8), N9(H9), C8(H8A), C12(H12), C14(H14), C15(H15),
 C16(H16), C20(H20), C22(H22), C23(H23), C24(H24), C28(H28), C30(H30), C31(H31),
  N5A(H5AA), N7A(H7A), N8A(H8AA), N9A(H9A), C8A(H8AB), C12A(H12A), C14A(H14A),
 C15A(H15A), C16A(H16A), C20A(H20A), C22A(H22A), C23A(H23A), C24A(H24A),
 C28A(H28A), C30A(H30A), C31A(H31A), N5B(H5B), N7B(H7B), N8B(H8B), N9B(H9B),
 C8B(H8BA), C12B(H12B), C14B(H14B), C15B(H15B), C16B(H16B), C20B(H20B),
 C22B(H22B), C23B(H23B), C24B(H24B), C28B(H28B), C30B(H30B), C31B(H31B),
 N5C(H5C), N7C(H7C), N8C(H8C), N9C(H9C), C8C(H8CA), C12C(H12C), C14C(H14C),
 C15C(H15C), C16C(H16C), C20C(H20C), C22C(H22C), C23C(H23C), C24C(H24C),
 C28C(H28C), C30C(H30C), C31C(H31C), N5D(H5D), N7D(H7D), N8D(H8D), N9D(H9D),
 C8D(H8DA), C12D(H12D), C14D(H14D), C15D(H15D), C16D(H16D), C20D(H20D),
 C22D(H22D), C23D(H23D), C24D(H24D), C28D(H28D), C30D(H30D), C31D(H31D),
 N5E(H5E), N7E(H7E), N8E(H8E), N9E(H9E), C8E(H8EA), C12E(H12E), C14E(H14E),
 C15E(H15E), C16E(H16E), C20E(H20E), C22E(H22E), C23E(H23E), C24E(H24E),
 C28E(H28E), C30E(H30E), C31E(H31E)
7.d Idealised Me refined as rotating group:
 C37(H37P,H37Q,H37R), C38(H38P,H38Q,H38R), C40(H40P,H40Q,H40R), C41(H41P,H41Q,
 H41R), C42(H42P,H42Q,H42R), C34(H34M,H34N,H34O), C35(H35M,H35N,H35O), C36(H36M,
 H36N,H36O), C34A(H34P,H34Q,H34R), C35A(H35P,H35Q,H35R), C36A(H36P,H36Q,H36R),
 C37A(H37S,H37T,H37U), C38A(H38S,H38T,H38U), C40A(H40S,H40T,H40U), C41A(H41S,
 H41T,H41U), C42A(H42S,H42T,H42U), C34B(H34J,H34K,H34L), C35B(H35J,H35K,H35L),
 C36B(H36J,H36K,H36L), C37B(H37M,H37N,H37O), C38B(H38M,H38N,H38O), C40B(H40M,
 H40N,H40O), C41B(H41M,H41N,H41O), C42B(H42M,H42N,H42O), C34C(H34S,H34T,H34U),
 C35C(H35S,H35T,H35U), C36C(H36S,H36T,H36U), C37C(H37V,H37W,H37X), C38C(H38V,
 H38W,H38X), C40C(H40V,H40W,H40X), C41C(H41V,H41W,H41X), C42C(H42V,H42W,H42X),
 C34D(H34G,H34H,H34I), C35D(H35G,H35H,H35I), C36D(H36G,H36H,H36I), C40D(H40G,
 H40H,H40I), C42D(H42G,H42H,H42I), C40G(H40J,H40K,H40L), C42G(H42J,H42K,H42L),
 C37F(H37A,H37B,H37C), C38F(H38A,H38B,H38C), C40F(H40A,H40B,H40C), C41F(H41A,
 H41B,H41C), C34E(H34A,H34B,H34C), C35E(H35A,H35B,H35C), C36E(H36A,H36B,H36C),
 C37E(H37D,H37E,H37F), C38E(H38D,H38E,H38F), C40E(H40D,H40E,H40F), C41E(H41D,
 H41E,H41F), C42E(H42D,H42E,H42F), C34F(H34D,H34E,H34F), C35F(H35D,H35E,H35F),
 C36F(H36D,H36E,H36F)
;
_shelx_res_checksum              77263
_shelx_hkl_checksum              34686
_shelx_fab_checksum              15887
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'