Enantioselective Total Synthesis of (+)-Wortmannin.
Guo, Yinliang; Quan, Tianfei; Lu, Yandong; Luo, Tuoping; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b02515

data_4126026
_publ_section_title
;
 Enantioselective Total Synthesis of (+)-Wortmannin.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b02515
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H22 O7'
_chemical_formula_sum            'C21 H22 O7'
_chemical_formula_weight         386.38
_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
_audit_creation_date             2016-12-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.07084(10)
_cell_length_b                   12.29131(12)
_cell_length_c                   13.30647(14)
_cell_measurement_reflns_used    42255
_cell_measurement_temperature    100.02(11)
_cell_measurement_theta_max      76.5390
_cell_measurement_theta_min      3.2710
_cell_volume                     1810.68(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.02(11)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega -115.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -57.0000  -90.0000 104

  2 omega  -40.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -57.0000  120.0000 29

  3 omega  -60.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056   57.0000 -120.0000 93

  4 omega -115.00  -43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -57.0000  120.0000 72

  5 omega  -61.00  -16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -38.0000    0.0000 45

  6 omega -124.00  -35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  178.0000 -150.0000 89

  7 omega -111.00  -69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -38.0000    0.0000 42

  8 omega   66.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6056  178.0000 -150.0000 62

  9 omega    7.00   32.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   88.0000    4.4128 25

 10 omega   12.00   39.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   83.0000   93.2577 27

 11 omega   13.00   38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   83.0000  171.7427 25

 12 omega   17.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   81.0000  -84.8227 25

 13 omega   17.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000   51.9647 25

 14 omega   17.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000  -22.5761 25

 15 omega   18.00   43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  152.5229 25

 16 omega   22.00   47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   78.0000 -127.9957 25

 17 omega   30.00   56.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000 -178.5474 26

 18 omega   31.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000  -26.0499 26

 19 omega   38.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000 -126.1154 26

 20 omega   34.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000  126.8746 26

 21 omega   34.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000   -9.1244 26

 22 omega  109.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000 -169.9596 37

 23 omega   35.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   74.0000   87.9350 25

 24 omega   36.00   61.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000   34.0804 25

 25 omega   34.00   61.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000 -169.9596 27

 26 omega   38.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   77.0000   -2.3286 31

 27 omega   90.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   58.0000  160.7430 59

 28 omega   46.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   58.0000  160.7430 32

 29 omega   45.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   70.0000   48.5883 29

 30 omega  103.00  152.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   74.0000  -86.7130 49

 31 omega   43.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   74.0000  -86.7130 31

 32 omega   44.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   71.0000 -114.9166 26

 33 omega   49.00   81.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       80.0000   65.0000 -162.8400 32

 34 omega   52.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       84.0000   76.0000   64.9615 26

 35 omega   61.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.0000   64.0000   81.3779 26

 36 omega   62.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.0000   61.0000 -115.0194 30

 37 omega   69.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   65.0000    0.7287 29

 38 omega   81.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   70.0000   16.2413 25

 39 omega   79.00  161.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -150.0000 82

 40 omega   46.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 70

 41 omega   79.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000    0.0000 98

 42 omega   80.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  120.0000 28

 43 omega   79.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -60.0000 99

 44 omega   65.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  -90.0000 48

 45 omega   33.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000 -150.0000 66

 46 omega   41.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000   90.0000 61

 47 omega   79.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -90.0000 67

 48 omega   35.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   30.0000 40

 49 omega   84.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 25

 50 omega   83.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -60.0000 65

 51 omega   79.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  150.0000 26

 52 omega   79.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   30.0000 74

 53 omega   82.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   65.0000  -87.4644 32

 54 omega   29.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -30.0000 74

 55 omega   83.00  162.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -30.0000 79

 56 omega  110.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   90.0000 37

 57 omega   84.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -180.0000 25

 58 omega   85.00  172.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  120.0000 87

 59 omega   79.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   90.0000 25

 60 omega   79.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -180.0000 99

 61 omega   85.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  150.0000 91

 62 omega   79.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   60.0000 31

 63 omega   79.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -120.0000 98

 64 omega   29.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  150.0000 76

 65 omega  114.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   60.0000 63

 66 omega   35.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -90.0000 54

 67 omega -131.00  -35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056 -178.0000  -60.0000 96

 68 omega    1.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6056  -99.0000    0.0000 82

 69 omega   55.00  129.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6056 -178.0000  -30.0000 74

 70 omega    9.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   83.0000   93.2577 31

 71 omega    6.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   89.0000  -58.7984 27

 72 omega   18.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  152.5229 28

 73 omega   17.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000 -171.5982 28

 74 omega   17.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   81.0000   29.0865 29

 75 omega   22.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   78.0000 -127.9957 27

 76 omega   27.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  -31.5415 111

 77 omega   34.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000  126.8746 113

 78 omega   35.00  145.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   74.0000   87.9350 110

 79 omega   38.00  151.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   77.0000   -2.3286 113

 80 omega   41.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   63.0000  -60.9243 106

 81 omega   46.00  150.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   58.0000  160.7430 104

 82 omega   44.00  152.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   70.0000   48.5883 108

 83 omega   43.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   74.0000  -86.7130 110

 84 omega   44.00  152.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   71.0000 -114.9166 108

 85 omega   49.00  155.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       80.0000   65.0000 -162.8400 106

 86 omega   57.00  150.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  -90.0000 93

 87 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -150.0000 95

 88 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   60.0000 95

 89 omega   82.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000   30.0000 96

 90 omega   85.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  -90.0000 93

 91 omega   35.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  120.0000 81

 92 omega  100.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000   90.0000 78

 93 omega   85.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -180.0000 93

 94 omega   38.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -150.0000 60

 95 omega  100.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000  -30.0000 78

 96 omega   35.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  -90.0000 81

 97 omega   35.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  -90.0000 56

 98 omega   38.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   60.0000 60

 99 omega   79.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -180.0000 99

100 omega   81.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   70.0000   -9.7349 97

101 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -30.0000 95

102 omega   29.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -60.0000 80

103 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  120.0000 95
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1178880000
_diffrn_orient_matrix_UB_12      0.0665097000
_diffrn_orient_matrix_UB_13      0.0027354000
_diffrn_orient_matrix_UB_21      0.0712633000
_diffrn_orient_matrix_UB_22      0.1007163000
_diffrn_orient_matrix_UB_23      0.0352435000
_diffrn_orient_matrix_UB_31      0.0198126000
_diffrn_orient_matrix_UB_32      0.0338669000
_diffrn_orient_matrix_UB_33      -0.1102143000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_unetI/netI     0.0104
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            69700
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.083
_diffrn_reflns_theta_min         4.898
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.890
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.05693
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.417
_exptl_crystal_description
;
;
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.178
_refine_diff_density_min         -0.171
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1615 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3794
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0260
_refine_ls_R_factor_gt           0.0259
_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^)+(0.0416P)^2^+0.3011P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0678
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3774
_reflns_number_total             3794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b02515_si_003.cif
_cod_data_source_block           exp_8208
_cod_database_code               4126026
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C21 O22 O7'
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.842
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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:
 C12(H12), C11(H11), C2(H2), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C6(H6A,H6B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'