Organocatalytic Asymmetric Tandem Nazarov Cyclization/Semipinacol Rearrangement: Rapid Construction of Chiral Spiro[4.4]nonane-1,6-diones.
Yang, Bin-Miao; Cai, Pei-Jun; Tu, Yong-Qiang; Yu, Zhi-Xiang; Chen, Zhi-Min; Wang, Shuang-Hu; Wang, Shao-Hua; Zhang, Fu-Min; Journal of the American Chemical Society 137 (2015) 8344–8347; doi:10.1021/jacs.5b04049

data_4123871
_publ_section_title
;
 Organocatalytic Asymmetric Tandem Nazarov Cyclization/Semipinacol
 Rearrangement: Rapid Construction of Chiral Spiro[4.4]nonane-1,6-diones.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8344
_journal_page_last               8347
_journal_paper_doi               10.1021/jacs.5b04049
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         '2(C18 H20 O2)'
_chemical_formula_sum            'C36 H40 O4'
_chemical_formula_weight         536.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 112.740(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.4872(8)
_cell_length_b                   10.2566(5)
_cell_length_c                   13.2057(9)
_cell_measurement_reflns_used    6581
_cell_measurement_temperature    294.39(10)
_cell_measurement_theta_max      69.6650
_cell_measurement_theta_min      3.6200
_cell_volume                     1434.95(18)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.39(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
  1 omega  -15.00   31.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 46

  2 omega  -30.00    9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  102.0000 -114.0000 39

  3 omega   35.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 28

  4 omega   23.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   30.0000 97

  5 omega   27.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  150.0000 57

  6 omega   39.00   67.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000 -150.0000 28

  7 omega    7.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000  -90.0000 91

  8 omega   38.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000    0.0000 27

  9 omega  107.00  175.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  -60.0000 68

 10 omega   37.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   90.0000 58

 11 omega   40.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -150.0000 52

 12 omega   65.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -120.0000 28

 13 omega  121.00  154.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -30.0000 33

 14 omega   86.00  161.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000    0.0000 75

 15 omega  115.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000    0.0000 63

 16 omega   36.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000   30.0000 43

 17 omega  110.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -30.0000 43

 18 omega  -55.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   60.0000 40

 19 omega   -9.00   21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   60.0000 30

 20 omega   24.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000 -180.0000 33

 21 omega   51.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  150.0000 26

 22 omega  -13.00   13.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000  -30.0000 26

 23 omega   46.00  123.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  120.0000 77

 24 omega   23.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -30.0000 26

 25 omega   37.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -38.0000 -180.0000 42

 26 omega  -16.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -38.0000 -180.0000 41

 27 omega   72.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000    0.0000 26

 28 omega   21.00   72.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000  -30.0000 51

 29 omega   91.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   90.0000 26

 30 omega  116.00  168.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 52

 31 omega  104.00  133.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   30.0000 29

 32 omega   76.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 33 omega   84.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   90.0000 26

 34 omega  153.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  150.0000 25

 35 omega   92.00  121.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  120.0000 29

 36 omega   82.00  144.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000 -180.0000 62

 37 omega  137.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   90.0000 39

 38 omega   63.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 50

 39 omega   89.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  150.0000 25

 40 omega   81.00  155.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  120.0000 74

 41 omega   76.00  101.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 25

 42 omega  115.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   90.0000 38

 43 omega   84.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  120.0000 25

 44 omega   76.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 45 omega   82.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000  150.0000 26

 46 omega   85.00  122.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   12.0000   90.0000 37
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0516295000
_diffrn_orient_matrix_UB_12      0.0550838000
_diffrn_orient_matrix_UB_13      -0.1177129000
_diffrn_orient_matrix_UB_21      0.0918480000
_diffrn_orient_matrix_UB_22      -0.0875954000
_diffrn_orient_matrix_UB_23      -0.0286414000
_diffrn_orient_matrix_UB_31      -0.1000612000
_diffrn_orient_matrix_UB_32      -0.1089201000
_diffrn_orient_matrix_UB_33      -0.0367571000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11362
_diffrn_reflns_theta_full        69.60
_diffrn_reflns_theta_max         69.60
_diffrn_reflns_theta_min         3.63
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.624
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54481
_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            'clear light colourless'
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.33
_refine_diff_density_max         1.214
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.3(4)
_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     370
_refine_ls_number_reflns         5153
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0818
_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^)+(0.1637P)^2^+0.8387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2257
_refine_ls_wR_factor_ref         0.2277
_reflns_number_gt                5015
_reflns_number_total             5153
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b04049_si_004.cif
_cod_data_source_block           yangbm0929_2
_cod_depositor_comments
'Adding full bibliography for 4123869--4123871.cif.'
_cod_original_cell_volume        1434.95(15)
_cod_database_code               4123871
_reflns_odcompleteness_completeness 99.30
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C22'-C23
 1.5 with sigma of 0.02
 C21-C22'
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C22') \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H21A(0.4) H21B(0.4) H21C(0.6) H21D(0.6) H23A(0.4) H23B(0.4)
 H23C(0.6) H23D(0.6) C22'(0.4) H22A(0.4) H22B(0.4) C22(0.6) H22C(0.6) H22D(0.6)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C24(H24), C25(H25), C2(H2), C6(H6), C7(H7)
5.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C21(H21C,H21D), C23(H23A,H23B), C23(H23C,H23D), C27(H27A,
 H27B), C28(H28A,H28B), C29(H29A,H29B), C22'(H22A,H22B), C22(H22C,H22D), C3(H3A,
 H3B), C4(H4A,H4B), C5(H5A,H5B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B)
5.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18)
;
_olex2_submission_special_instructions 'No special instructions were received'