Cycloaddition of Spiroepoxycyclohexa-2,4-dienones, Radical Cyclization and 1,3-Acyl Shift in Excited State: Aromatics to Sterpuren-4-one.
Sahu, Raghaba; Singh, Vishwakarma; The Journal of organic chemistry 82 (2017) 6268–6278; doi:10.1021/acs.joc.7b00867

data_4032754
_publ_section_title
;
 Cycloaddition of Spiroepoxycyclohexa-2,4-dienones, Radical Cyclization
 and 1,3-Acyl Shift in Excited State: Aromatics to Sterpuren-4-one.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6268
_journal_page_last               6278
_journal_paper_doi               10.1021/acs.joc.7b00867
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C17 H22 O4'
_chemical_formula_sum            'C17 H22 O4'
_chemical_formula_weight         290.34
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-07-11
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2015.10.28 svn.r3245 for OlexSys, GUI svn.r5128)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.0478(4)
_cell_length_b                   7.17097(13)
_cell_length_c                   21.1937(4)
_cell_measurement_reflns_used    12785
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.7240
_cell_measurement_theta_min      4.4190
_cell_volume                     3046.85(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -191.00 -11.00   1.00    6.00    -- -101.00   0.00-108.00  180
  2  \w   -122.00 -24.00   1.00    6.00    --  -32.00 -72.00 108.00   98
  3  \w   -122.00 -29.00   1.00    6.00    -- -101.00  72.00-108.00   93
  4  \w   -135.00-101.00   1.00    6.00    -- -101.00  72.00  36.00   34
  5  \w   -117.00 -38.00   1.00    6.00    --  -32.00 -72.00-108.00   79
  6  \w    -96.00 -24.00   1.00    6.00    -- -101.00  72.00 108.00   72
  7  \w   -151.00 -11.00   1.00    6.00    -- -101.00   0.00 -36.00  140
  8  \w   -191.00 -77.00   1.00    6.00    -- -101.00 -72.00 -36.00  114
  9  \w    -97.00  22.00   1.00    6.00    --  -32.00   0.00-180.00  119
 10  \w   -126.00 -30.00   1.00    6.00    -- -101.00  72.00-180.00   96
 11  \w    -81.00 -51.00   1.00    6.00    -- -101.00  72.00 -36.00   30
 12  \w    -97.00 -67.00   1.00    6.00    -- -101.00 -72.00 108.00   30
 13  \w   -191.00 -97.00   1.00    6.00    -- -101.00   0.00 108.00   94
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0156797000
_diffrn_orient_matrix_UB_12      0.0709894000
_diffrn_orient_matrix_UB_13      -0.0669361000
_diffrn_orient_matrix_UB_21      0.0618882000
_diffrn_orient_matrix_UB_22      -0.1026236000
_diffrn_orient_matrix_UB_23      -0.0254809000
_diffrn_orient_matrix_UB_31      -0.0428584000
_diffrn_orient_matrix_UB_32      -0.1748114000
_diffrn_orient_matrix_UB_33      -0.0122151000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0684
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            22185
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        64.998
_diffrn_reflns_theta_max         64.998
_diffrn_reflns_theta_min         4.411
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.724
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       plate
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.162
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.490
_refine_diff_density_rms         0.147
_refine_ls_abs_structure_details
;
 Flack x determined using 2133 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         5096
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.175
_refine_ls_R_factor_all          0.0563
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0942P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1411
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.969
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                4828
_reflns_number_total             5096
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00867_si_002.cif
_cod_data_source_block           vks-rs-add_cu
_cod_database_code               4032754
_chemical_oxdiff_formula         'C17 H22 O4'
_reflns_odcompleteness_completeness 98.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.74
_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:
 C4(H4), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C31(H31A,H31B), C27(H27A,H27B), C32(H32A,H32B),
 C5(H5A,H5B), C23(H23A,H23B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C24(H24), C13(H13), C28(H28)
2.d X=CH2 refined with riding coordinates:
 C29(H29A,H29B), C14(H14A,H14B)
2.e Idealised Me refined as rotating group:
 C00G(H00A,H00B,H00C), C26(H26A,H26B,H26C), C33(H33A,H33B,H33C), C30(H30A,H30B,
 H30C), C1(H1A,H1B,H1C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              56887
_shelx_hkl_checksum              45837
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.625
_oxdiff_exptl_absorpt_empirical_full_min 0.543