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_1548228
_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_absolute_configuration unk
_chemical_formula_moiety         'C14 H18 O2'
_chemical_formula_sum            'C14 H18 O2'
_chemical_formula_weight         218.28
_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
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            16
_cell_length_a                   15.2428(11)
_cell_length_b                   15.4175(16)
_cell_length_c                   21.1538(12)
_cell_measurement_reflns_used    2668
_cell_measurement_temperature    298.06(14)
_cell_measurement_theta_max      22.6390
_cell_measurement_theta_min      3.5420
_cell_volume                     4971.3(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
;
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      298.06(14)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9960
_diffrn_measured_fraction_theta_max 0.9045
_diffrn_measurement_details
;
  1 omega -103.00  -77.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000  -90.0000 17

  2 omega  -90.00  -55.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000   90.0000 23

  3 omega   51.00   78.00   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  -90.0000 18

  4 omega  -36.00   88.50   1.5000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512    0.0000 -180.0000 83
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0109414000
_diffrn_orient_matrix_UB_12      -0.0403114000
_diffrn_orient_matrix_UB_13      -0.0140595000
_diffrn_orient_matrix_UB_21      0.0420792000
_diffrn_orient_matrix_UB_22      -0.0017532000
_diffrn_orient_matrix_UB_23      -0.0143284000
_diffrn_orient_matrix_UB_31      0.0167027000
_diffrn_orient_matrix_UB_32      -0.0220515000
_diffrn_orient_matrix_UB_33      0.0268871000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0894
_diffrn_reflns_av_unetI/netI     0.1303
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16709
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.13
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.076
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38609
_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    1.167
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.179
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.4(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.937
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     589
_refine_ls_number_reflns         8154
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.937
_refine_ls_R_factor_all          0.1499
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0358P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1695
_reflns_number_gt                3626
_reflns_number_total             8154
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ncomms8332-s5.cif
_cod_data_source_block           jiaozhw0504
_cod_database_code               1548228
_reflns_odcompleteness_completeness 99.60
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C23(H23), C37(H37), C51(H51)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C15(H15A,H15B), C22(H22A,H22B), C29(H29A,H29B),
 C36(H36A,H36B), C43(H43A,H43B), C50(H50A,H50B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C17(H17), C18(H18), C19(H19), C20(H20),
 C31(H31), C32(H32), C33(H33), C35(H35), C45(H45), C46(H46), C47(H47), C48(H48)
2.d X=CH2 refined with riding coordinates:
 C13(H13A,H13B), C26(H26A,H26B), C40(H40A,H40B), C54(H54A,H54B)
2.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C)
2.f Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4A), O6(H6A), O8(H8)
;