Construction of the [6,5,7,5] Tetracyclic Core of Calyciphylline A Type Alkaloids via a Tandem Semipinacol Rearrangement/Nicholas Reaction.
Shao, Hui; Bao, Wen; Jing, Ze-Ran; Wang, Yun-Peng; Zhang, Fu-Min; Wang, Shao-Hua; Tu, Yong-Qiang; Organic letters 19 (2017) 4648–4651; doi:10.1021/acs.orglett.7b02274

data_1547036
_publ_section_title
;
 Construction of the [6,5,7,5] Tetracyclic Core of Calyciphylline A Type
 Alkaloids via a Tandem Semipinacol Rearrangement/Nicholas Reaction.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4648
_journal_page_last               4651
_journal_paper_doi               10.1021/acs.orglett.7b02274
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C30 H49 N O6 S Si'
_chemical_formula_sum            'C30 H49 N O6 S Si'
_chemical_formula_weight         579.85
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                101.972(4)
_cell_angle_beta                 99.482(4)
_cell_angle_gamma                91.091(4)
_cell_formula_units_Z            4
_cell_length_a                   12.6657(5)
_cell_length_b                   13.8437(7)
_cell_length_c                   19.3886(9)
_cell_measurement_reflns_used    2570
_cell_measurement_temperature    292.7(6)
_cell_measurement_theta_max      20.3790
_cell_measurement_theta_min      3.7540
_cell_volume                     3275.2(3)
_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      292.7(6)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   -3.00   24.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -99.0000    0.0000 27

  2 omega -100.00  -73.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  178.0000   30.0000 27

  3 omega    3.00   95.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   77.0000    0.0000 92

  4 omega   47.00   73.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  178.0000  -30.0000 26

  5 omega  -12.00   62.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -99.0000 -150.0000 74

  6 omega    4.00   45.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   57.0000  -30.0000 41

  7 omega  -44.00   95.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   19.0000 -180.0000 139
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0188611000
_diffrn_orient_matrix_UB_12      -0.0397094000
_diffrn_orient_matrix_UB_13      0.0135032000
_diffrn_orient_matrix_UB_21      -0.0000773000
_diffrn_orient_matrix_UB_22      -0.0324812000
_diffrn_orient_matrix_UB_23      -0.0335208000
_diffrn_orient_matrix_UB_31      0.0536447000
_diffrn_orient_matrix_UB_32      -0.0109436000
_diffrn_orient_matrix_UB_33      0.0116390000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0523
_diffrn_reflns_av_unetI/netI     0.1119
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23436
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         3.321
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.175
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94518
_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    1.176
_exptl_crystal_description       block
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.515
_refine_diff_density_min         -0.461
_refine_diff_density_rms         0.052
_refine_ls_extinction_coef       0.0021(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     720
_refine_ls_number_reflns         12874
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1942
_refine_ls_R_factor_gt           0.0889
_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^)+(0.1213P)^2^+0.3269P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.3035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5230
_reflns_number_total             12874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02274_si_005.cif
_cod_data_source_block           jingzr_0515
_cod_database_code               1547036
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O N'
_reflns_odcompleteness_completeness 99.79
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C53) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(Si2) \\sim Ueq:
with sigma of 0.04 and sigma for terminal atoms of 0.05
Uanis(C53) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(Si2) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C11(H11), C31(H31), C34(H34), C39(H39)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,
 H12B), C13(H13A,H13B), C22(H22A,H22B), C23(H23A,H23B), C32(H32A,H32B),
 C33(H33A,H33B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B),
  C41(H41A,H41B), C50(H50A,H50B), C51(H51A,H51B)
3.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C19(H19), C20(H20), C44(H44), C45(H45), C47(H47), C48(H48)
3.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C14(H14A,H14B,H14C), C21(H21A,H21B,
 H21C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C30(H30A,
 H30B,H30C), C0AA(H0AA,H0AB,H0AC), C1AA(H1AA,H1AB,H1AC), C42(H42A,H42B,H42C),
 C49(H49A,H49B,H49C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              7130
_shelx_hkl_checksum              31187
_olex2_date_sample_data_collection 2017-05-15
_olex2_submission_special_instructions 'No special instructions were received'