Spirocyclopropanation Reaction of para-Quinone Methides with Sulfonium Salts: The Synthesis of Spirocyclopropanyl para-Dienones.
Zhang, Xiang-Zhi; Du, Ji-Yuan; Deng, Yu-Hua; Chu, Wen-Dao; Yan, Xu; Yu, Ke-Yin; Fan, Chun-An; The Journal of organic chemistry 81 (2016) 2598–2606; doi:10.1021/acs.joc.5b02725

data_4036555
_publ_section_title
;
 Spirocyclopropanation Reaction of para-Quinone Methides with Sulfonium
 Salts: The Synthesis of Spirocyclopropanyl para-Dienones.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2598
_journal_page_last               2606
_journal_paper_doi               10.1021/acs.joc.5b02725
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C25 H32 O3'
_chemical_formula_sum            'C25 H32 O3'
_chemical_formula_weight         380.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-16
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:06:00, GUI svn.r4458)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.504(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.4475(11)
_cell_length_b                   10.8201(9)
_cell_length_c                   17.2007(12)
_cell_measurement_reflns_used    1877
_cell_measurement_temperature    294.13(10)
_cell_measurement_theta_max      22.4470
_cell_measurement_theta_min      3.5760
_cell_volume                     2296.8(3)
_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      294.13(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9972
_diffrn_measured_fraction_theta_max 0.8817
_diffrn_measurement_details
;
  1 omega -103.00  -58.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000  150.0000 30

  2 omega  -84.00  -57.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000 -150.0000 18

  3 omega   46.00  100.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  178.0000 -120.0000 36

  4 omega  -15.00   99.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512    0.0000 -180.0000 76
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0338646000
_diffrn_orient_matrix_UB_12      0.0258244000
_diffrn_orient_matrix_UB_13      -0.0259742000
_diffrn_orient_matrix_UB_21      -0.0279212000
_diffrn_orient_matrix_UB_22      0.0569721000
_diffrn_orient_matrix_UB_23      0.0007004000
_diffrn_orient_matrix_UB_31      0.0371503000
_diffrn_orient_matrix_UB_32      0.0194346000
_diffrn_orient_matrix_UB_33      0.0325364000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0664
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            8651
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.04
_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  0.37808
_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    1.100
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.256
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         4516
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1248
_refine_ls_R_factor_gt           0.0720
_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^)+(0.0938P)^2^+0.2056P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1749
_refine_ls_wR_factor_ref         0.2240
_reflns_number_gt                2484
_reflns_number_total             4516
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5b02725_si_002.cif
_cod_data_source_block           zhangxzh0915
_cod_database_code               4036555
_reflns_odcompleteness_completeness 99.72
_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:
 C7(H7), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;