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_4036557
_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         'C26 H36 O4'
_chemical_formula_sum            'C26 H36 O4'
_chemical_formula_weight         412.55
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-11-04
_audit_creation_method
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Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
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_cell_angle_alpha                90
_cell_angle_beta                 99.987(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2390(4)
_cell_length_b                   19.3276(7)
_cell_length_c                   12.6233(6)
_cell_measurement_reflns_used    2631
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      22.5670
_cell_measurement_theta_min      3.5090
_cell_volume                     2460.24(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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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 0.9979
_diffrn_measured_fraction_theta_max 0.8928
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0081929000
_diffrn_orient_matrix_UB_12      0.0216599000
_diffrn_orient_matrix_UB_13      -0.0460491000
_diffrn_orient_matrix_UB_21      -0.0185499000
_diffrn_orient_matrix_UB_22      0.0277784000
_diffrn_orient_matrix_UB_23      0.0309423000
_diffrn_orient_matrix_UB_31      0.0673853000
_diffrn_orient_matrix_UB_32      0.0102720000
_diffrn_orient_matrix_UB_33      0.0132578000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            10546
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_min         2.920
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.073
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23297
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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    1.114
_exptl_crystal_description       needle
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.3500
_exptl_crystal_size_mid          0.3200
_exptl_crystal_size_min          0.2100
_refine_diff_density_max         0.148
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.0053(14)
_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   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         4848
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.1110
_refine_ls_R_factor_gt           0.0654
_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^)+(0.0751P)^2^+0.5269P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1695
_refine_ls_wR_factor_ref         0.2047
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2750
_reflns_number_total             4848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02725_si_004.cif
_cod_data_source_block           zhangxzh1104_2
_cod_original_cell_volume        2460.25(18)
_cod_database_code               4036557
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.79
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14)
2.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), C26(H26A,
 H26B,H26C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              99398
_shelx_hkl_checksum              95096