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_4036556
_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 H34 O4'
_chemical_formula_sum            'C25 H34 O4'
_chemical_formula_weight         398.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.275(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4772(12)
_cell_length_b                   37.395(5)
_cell_length_c                   6.0408(7)
_cell_measurement_reflns_used    1296
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.5900
_cell_measurement_theta_min      3.7690
_cell_volume                     2347.7(5)
_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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9919
_diffrn_measured_fraction_theta_max 0.8822
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0283667000
_diffrn_orient_matrix_UB_12      0.0171795000
_diffrn_orient_matrix_UB_13      -0.0016220000
_diffrn_orient_matrix_UB_21      -0.0616601000
_diffrn_orient_matrix_UB_22      0.0079964000
_diffrn_orient_matrix_UB_23      -0.0043095000
_diffrn_orient_matrix_UB_31      0.0067759000
_diffrn_orient_matrix_UB_32      0.0005222000
_diffrn_orient_matrix_UB_33      0.1183841000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.1024
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            8267
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         3.269
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69844
_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    1.127
_exptl_crystal_description       needle
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.2900
_exptl_crystal_size_mid          0.1200
_exptl_crystal_size_min          0.1100
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.0057(15)
_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   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         4596
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1650
_refine_ls_R_factor_gt           0.0923
_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^)+(0.0712P)^2^+1.4727P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1996
_refine_ls_wR_factor_ref         0.2528
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2249
_reflns_number_total             4596
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02725_si_005.cif
_cod_data_source_block           zhangxzh1104
_cod_database_code               4036556
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.19
_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, All O(H) groups
2. Restrained distances
 H1-O1
 0.85 with sigma of 0.02
 H1-C4
 2 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14)
3.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C25(H25A,H25B,H25C)
3.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              83114
_shelx_hkl_checksum              90610