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_4123869
_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_formula_moiety         'C19 H22 O2'
_chemical_formula_sum            'C19 H22 O2'
_chemical_formula_weight         282.36
_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     iterative
_audit_creation_date             2013-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4715)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.128(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.2548(3)
_cell_length_b                   10.0794(2)
_cell_length_c                   10.0211(3)
_cell_measurement_reflns_used    5876
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7050
_cell_measurement_theta_min      5.6900
_cell_volume                     782.87(4)
_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, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -63.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -38.0000  -30.0000 29

  2 omega  -71.00  -38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000   90.0000 33

  3 omega   33.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000    0.0000 30

  4 omega  -58.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   50.0000  150.0000 49

  5 omega -106.00  -42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000 -170.0000  166.0000 64

  6 omega  -41.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000   60.0000 26

  7 omega    1.00   28.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000    0.0000 27

  8 omega   39.00  126.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000 -150.0000 87

  9 omega   33.00  125.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000    0.0000 92

 10 omega   25.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000 -125.0000   60.0000 91

 11 omega   46.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -75.0000 -131.7661 36

 12 omega   -6.00   43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000  -30.0000 49

 13 omega  -10.00   16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -75.0000 -131.7661 26

 14 omega   27.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -38.0000   60.0000 26

 15 omega   42.00  100.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000   90.0000 58

 16 omega   43.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000   60.0000 33

 17 omega  107.00  133.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000 -120.0000 26

 18 omega   39.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  -90.0000 71

 19 omega   51.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000 -150.0000 32

 20 omega  116.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   50.0000  150.0000 57

 21 omega   41.00   72.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -38.0000 -150.0000 31

 22 omega   87.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000   30.0000 29

 23 omega   55.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000 -120.0000 38

 24 omega   87.00  151.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000   30.0000 64

 25 omega   41.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000   30.0000 29

 26 omega   88.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000 -150.0000 28

 27 omega   43.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  120.0000 26

 28 omega   57.00  130.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000    0.0000 73

 29 omega  149.00  174.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000 -120.0000 25

 30 omega  101.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -30.0000 76

 31 omega   85.00  125.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000  120.0000 40

 32 omega  101.00  129.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -60.0000 28

 33 omega   84.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  -30.0000 32

 34 omega  101.00  157.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   25.0000  150.0000 56

 35 omega   94.00  137.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000 -150.0000 43

 36 omega   63.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000 -150.0000 41

 37 omega   68.00  164.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   25.0000  -60.0000 96

 38 omega   49.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -38.0000    0.0000 29

 39 omega   37.00   94.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  -60.0000 57

 40 omega   47.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000   30.0000 36

 41 omega   89.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000 -120.0000 25

 42 omega   79.00  154.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   25.0000  120.0000 75

 43 omega  -82.00  -57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -60.0000 25

 44 omega   16.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000 -115.0000  -50.0000 26

 45 omega   94.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000 -150.0000 26

 46 omega  153.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000 -150.0000 25

 47 omega   75.00  122.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000    0.0000 47

 48 omega   86.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   50.0000   30.0000 27

 49 omega  117.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000 -180.0000 26

 50 omega  -72.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000 -120.0000 105

 51 omega  -82.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000   60.0000 48

 52 omega -115.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  -90.0000 106

 53 omega -115.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   60.0000 106

 54 omega -112.00  -17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -63.0000 -180.0000 95

 55 omega -115.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  150.0000 106

 56 omega -115.00   -9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000    0.0000 106

 57 omega  -15.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000  150.0000 50
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0094909000
_diffrn_orient_matrix_UB_12      -0.1502618000
_diffrn_orient_matrix_UB_13      0.0296751000
_diffrn_orient_matrix_UB_21      0.1944199000
_diffrn_orient_matrix_UB_22      0.0125135000
_diffrn_orient_matrix_UB_23      0.0849926000
_diffrn_orient_matrix_UB_31      -0.0408116000
_diffrn_orient_matrix_UB_32      0.0248051000
_diffrn_orient_matrix_UB_33      0.1367609000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7909
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         70.076
_diffrn_reflns_theta_min         5.708
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.595
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75602
_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    1.198
_exptl_crystal_description       block
_exptl_crystal_F_000             304
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.27
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.139
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1333 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.09(9)
_refine_ls_extinction_coef       0.079(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         2945
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0374
_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^)+(0.0750P)^2^+0.0305P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                2893
_reflns_number_total             2945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04049_si_003.cif
_cod_data_source_block           yangbm_1122_cu
_cod_depositor_comments
'Adding full bibliography for 4123869--4123871.cif.'
_cod_original_cell_volume        782.87(5)
_cod_database_code               4123869
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 92.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Others
 Fixed Sof: H13A(0.8) H13B(0.8) H11C(0.2) H11D(0.2) H11A(0.8) H11B(0.8)
 H13C(0.2) H13D(0.2) C12(0.83) H12A(0.83) H12B(0.83) C1A(0.17) H1AA(0.17)
 H1AB(0.17)
3.a Ternary CH refined with riding coordinates:
 C3(H3), C9(H9), C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13(H11C,H11D), C7(H7A,H7B), C11(H11A,H11B), C11(H13C,H13D),
 C4(H4A,H4B), C6(H6A,H6B), C12(H12A,H12B), C5(H5A,H5B), C1A(H1AA,H1AB)
3.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C19(H19), C16(H16), C17(H17), C18(H18)
;
_shelx_res_checksum              4352
_shelx_hkl_checksum              39446