Asymmetric Total Synthesis of (-)-Aspidophylline A.
Wang, Taimin; Duan, Xiaoguang; Zhao, Hua; Zhai, Shengxian; Tao, Cheng; Wang, Huifei; Li, Yun; Cheng, Bin; Zhai, Hongbin; Organic letters 19 (2017) 1650–1653; doi:10.1021/acs.orglett.7b00448

data_1545952
_publ_section_title
;
 Asymmetric Total Synthesis of (-)-Aspidophylline A.
;
_journal_issue                   7
_journal_name_full               'Organic letters'
_journal_page_first              1650
_journal_page_last               1653
_journal_paper_doi               10.1021/acs.orglett.7b00448
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C26 H38 N4 O4 Si'
_chemical_formula_sum            'C26 H38 N4 O4 Si'
_chemical_formula_weight         498.69
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-09
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.083(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.0702(18)
_cell_length_b                   10.9823(7)
_cell_length_c                   21.1910(12)
_cell_measurement_reflns_used    1909
_cell_measurement_temperature    290.90(10)
_cell_measurement_theta_max      22.4290
_cell_measurement_theta_min      3.8610
_cell_volume                     5767.5(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      290.90(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9969
_diffrn_measured_fraction_theta_max 0.8992
_diffrn_measurement_details
;
  1 omega -102.00  -58.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  178.0000  -60.0000 44

  2 omega  -16.00   18.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -99.0000  150.0000 34

  3 omega    3.00   29.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   38.0000  -60.0000 26

  4 omega   36.00   64.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -99.0000  -30.0000 28

  5 omega  -35.00   88.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867    0.0000   90.0000 123

  6 omega   77.00  102.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000   30.0000 25
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0168858000
_diffrn_orient_matrix_UB_12      -0.0504866000
_diffrn_orient_matrix_UB_13      -0.0003689000
_diffrn_orient_matrix_UB_21      0.0229884000
_diffrn_orient_matrix_UB_22      0.0383130000
_diffrn_orient_matrix_UB_23      0.0105291000
_diffrn_orient_matrix_UB_31      0.0022817000
_diffrn_orient_matrix_UB_32      -0.0125419000
_diffrn_orient_matrix_UB_33      0.0335909000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0697
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            12743
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.020
_diffrn_reflns_theta_min         3.282
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.117
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       block
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         5669
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1316
_refine_ls_R_factor_gt           0.0697
_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^)+(0.0782P)^2^+2.5663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.2063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2981
_reflns_number_total             5669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b00448_si_001.cif
_cod_data_source_block           wangtm_0106
_cod_original_cell_volume        5767.5(6)
_cod_database_code               1545952
_chemical_oxdiff_formula         'C H O N'
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C20'-C19'
 2.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C20') \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C21') \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C19') \\sim Ueq, Uanis(C18') \\sim Ueq,
Uanis(C17') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: H16A(0.7) H16B(0.7) H16C(0.7) H16D(0.3) H16E(0.3) H16F(0.3)
 Si1(0.7) C17(0.75) C18(0.65) H18A(0.65) H18B(0.65) H18C(0.65) C19(0.65)
 H19A(0.65) H19B(0.65) H19C(0.65) C20(0.7) H20A(0.7) H20B(0.7) H20C(0.7)
 C21(0.65) H21A(0.65) H21B(0.65) H21C(0.65) Si1'(0.3) C17'(0.25) C18'(0.35)
 H18D(0.35) H18E(0.35) H18F(0.35) C19'(0.35) H19D(0.35) H19E(0.35) H19F(0.35)
 C20'(0.3) H20D(0.3) H20E(0.3) H20F(0.3) C21'(0.35) H21D(0.35) H21E(0.35)
 H21F(0.35)
5.a Ternary CH refined with riding coordinates:
 C9(H9), C11(H11)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C14(H14A,H14B), C15(H15A,H15B)
5.c Me refined with riding coordinates:
 C16(H16A,H16B,H16C), C16(H16D,H16E,H16F)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5)
5.e X=CH2 refined with riding coordinates:
 C13(H13A,H13B)
5.f Idealised Me refined as rotating group:
 C2AA(H2AA,H2AB,H2AC), C3AA(H3AA,H3AB,H3AC), C4AA(H4AA,H4AB,H4AC), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C18'(H18D,H18E,H18F), C19'(H19D,H19E,H19F), C20'(H20D,H20E,H20F), C21'(H21D,
 H21E,H21F)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-01-09
_olex2_submission_special_instructions 'No special instructions were received'