Tandem Spirocyclopropanation/Rearrangement Reaction of Vinyl p-Quinone Methides with Sulfonium Salts: Synthesis of Spirocyclopentenyl p-Dienones.
Zhang, Xiang-Zhi; Deng, Yu-Hua; Gan, Kang-Ji; Yan, Xu; Yu, Ke-Yin; Wang, Fang-Xin; Fan, Chun-An; Organic letters 19 (2017) 1752–1755; doi:10.1021/acs.orglett.7b00516

data_1545959
_publ_section_title
;
 Tandem Spirocyclopropanation/Rearrangement Reaction of Vinyl p-Quinone
 Methides with Sulfonium Salts: Synthesis of Spirocyclopentenyl
 p-Dienones.
;
_journal_issue                   7
_journal_name_full               'Organic letters'
_journal_page_first              1752
_journal_page_last               1755
_journal_paper_doi               10.1021/acs.orglett.7b00516
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C27 H34 O3'
_chemical_formula_sum            'C27 H34 O3'
_chemical_formula_weight         406.54
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-12-02
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4866)
;
_cell_angle_alpha                98.404(9)
_cell_angle_beta                 92.358(9)
_cell_angle_gamma                94.506(8)
_cell_formula_units_Z            2
_cell_length_a                   9.8361(10)
_cell_length_b                   9.9871(10)
_cell_length_c                   12.5171(14)
_cell_measurement_reflns_used    1166
_cell_measurement_temperature    291.89(10)
_cell_measurement_theta_max      22.2010
_cell_measurement_theta_min      3.6590
_cell_volume                     1210.9(2)
_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      291.89(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -18.00   25.50   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3571  -99.0000 -120.0000 29

  2 omega   49.00   91.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946 -178.0000  -60.0000 28

  3 omega    6.00   40.50   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946  -57.0000  -30.0000 23

  4 omega   21.00   61.50   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946  -99.0000  120.0000 27

  5 omega   34.00   67.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946 -178.0000  -30.0000 22

  6 omega  -37.00   63.50   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946  -19.0000  -90.0000 67

  7 omega   -3.00   87.00   1.5000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946   38.0000  120.0000 60
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0653375000
_diffrn_orient_matrix_UB_12      0.0010997000
_diffrn_orient_matrix_UB_13      0.0219129000
_diffrn_orient_matrix_UB_21      -0.0275022000
_diffrn_orient_matrix_UB_22      -0.0479738000
_diffrn_orient_matrix_UB_23      -0.0445744000
_diffrn_orient_matrix_UB_31      0.0148995000
_diffrn_orient_matrix_UB_32      -0.0537543000
_diffrn_orient_matrix_UB_33      0.0286969000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0444
_diffrn_reflns_av_unetI/netI     0.0898
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_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            8457
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.35
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.071
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76731
_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_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.115
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.021(5)
_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   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     279
_refine_ls_number_reflns         4752
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1509
_refine_ls_R_factor_gt           0.0714
_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^)+(0.0752P)^2^+0.2066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1608
_refine_ls_wR_factor_ref         0.2233
_reflns_number_gt                2238
_reflns_number_total             4752
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b00516_si_001.cif
_cod_data_source_block           zhangxzh_1201
_cod_database_code               1545959
_reflns_odcompleteness_completeness 99.68
_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:
 C2(H2), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C26(H26a,H26b)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C10(H10), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24)
2.d Idealised Me refined as rotating group:
 C12(H12a,H12b,H12c), C13(H13a,H13b,H13c), C14(H14a,H14b,H14c), C16(H16a,H16b,
 H16c), C17(H17a,H17b,H17c), C18(H18a,H18b,H18c), C27(H27a,H27b,H27c)
;
_olex2_submission_special_instructions 'No special instructions were received'