Tandem C-H oxidation/cyclization/rearrangement and its application to asymmetric syntheses of (-)-brussonol and (-)-przewalskine E
Zhi-Wei Jiao; Yong-Qiang Tu; Qing Zhang; Wen-Xing Liu; Shu-Yu Zhang; Shao-Hua Wang; Fu-Min Zhang; Sen Jiang; Nature Communications 6 (2015) 7332–; doi:10.1038/ncomms8332

data_1548225
_publ_section_title
;
 Tandem C-H oxidation/cyclization/rearrangement and its application to
 asymmetric syntheses of (-)-brussonol and (-)-przewalskine E
;
_journal_name_full               'Nature Communications'
_journal_page_first              7332
_journal_paper_doi               10.1038/ncomms8332
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C24 H32 O2 Si'
_chemical_formula_sum            'C24 H32 O2 Si'
_chemical_formula_weight         380.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6184(3)
_cell_length_b                   16.5442(8)
_cell_length_c                   18.1572(8)
_cell_measurement_reflns_used    2437
_cell_measurement_temperature    294.90(15)
_cell_measurement_theta_max      25.7890
_cell_measurement_theta_min      3.8040
_cell_volume                     2288.54(17)
_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
;
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, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      294.90(15)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9967
_diffrn_measured_fraction_theta_max 0.7564
_diffrn_measurement_details
;
  1 omega  -42.00   -9.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700   19.0000   90.0000 33

  2 omega  -83.00  -48.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -77.0000   90.0000 35

  3 omega -101.00  -57.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000  120.0000 44

  4 omega   34.00  106.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075 -178.0000   30.0000 72

  5 omega  -22.00    3.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       22.8075  -57.0000 -120.0000 25
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0081150000
_diffrn_orient_matrix_UB_12      -0.0311321000
_diffrn_orient_matrix_UB_13      0.0266499000
_diffrn_orient_matrix_UB_21      0.0922869000
_diffrn_orient_matrix_UB_22      0.0000738000
_diffrn_orient_matrix_UB_23      0.0050511000
_diffrn_orient_matrix_UB_31      -0.0088381000
_diffrn_orient_matrix_UB_32      0.0295075000
_diffrn_orient_matrix_UB_33      0.0281089000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            8377
_diffrn_reflns_point_group_measured_fraction_full 0.860
_diffrn_reflns_point_group_measured_fraction_max 0.756
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.532
_diffrn_reflns_theta_min         2.900
_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  0.90522
_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_density_diffrn    1.105
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 973 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.05(9)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         4403
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0656
_refine_ls_R_factor_gt           0.0489
_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^)+(0.0540P)^2^+0.1160P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1184
_reflns_Friedel_coverage         0.465
_reflns_Friedel_fraction_full    0.675
_reflns_Friedel_fraction_max     0.554
_reflns_number_gt                3472
_reflns_number_total             4403
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms8332-s2.cif
_cod_data_source_block           jiaozhw0604
_cod_database_code               1548225
_reflns_odcompleteness_completeness 99.67
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C11(H11), C18(H18), C15(H15), C14(H14), C7(H7), C6(H6), C5(H5),
 C17(H17), C16(H16)
2.d X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C)
;
_shelx_hkl_checksum              17259
_shelx_res_checksum              26281
_shelxl_version_number           2013-2