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_4032560
_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         'C20 H24 N4 O4'
_chemical_formula_sum            'C20 H24 N4 O4'
_chemical_formula_weight         384.43
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-01-12
_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                 117.18(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.300(4)
_cell_length_b                   7.8692(10)
_cell_length_c                   16.258(3)
_cell_measurement_reflns_used    1906
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.4990
_cell_measurement_theta_min      2.6470
_cell_volume                     1968.9(8)
_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      150.0
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -110.00  44.00   0.50   16.00    --  -20.00   0.00-108.00  308
  2  \w    -44.00  14.50   0.50   16.00    --  -20.00 -72.00-180.00  117
;
_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      -0.0025721000
_diffrn_orient_matrix_UB_12      -0.0785147000
_diffrn_orient_matrix_UB_13      0.0200946000
_diffrn_orient_matrix_UB_21      -0.0458120000
_diffrn_orient_matrix_UB_22      0.0003091000
_diffrn_orient_matrix_UB_23      -0.0269438000
_diffrn_orient_matrix_UB_31      0.0042158000
_diffrn_orient_matrix_UB_32      -0.0443155000
_diffrn_orient_matrix_UB_33      -0.0357103000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0875
_diffrn_reflns_av_unetI/netI     0.1460
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7627
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.506
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.092
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32528
_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            'yellowish orange'
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       plate
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.575
_refine_diff_density_min         -0.568
_refine_diff_density_rms         0.207
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3466
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.1646
_refine_ls_R_factor_gt           0.0743
_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^)+(0.1019P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1715
_refine_ls_wR_factor_ref         0.2590
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1822
_reflns_number_total             3466
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00867_si_003.cif
_cod_data_source_block           vks-rs-2-4-dnp_mo
_cod_depositor_comments          'Adding full bibliography for 4032560.cif.'
_cod_original_cell_volume        1969.0(8)
_cod_database_code               4032560
_chemical_oxdiff_formula         C20H24N4O4
_reflns_odcompleteness_completeness 87.22
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.09
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C8(H8A,H8B), C15(H15A,H15B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C5(H5), C4(H4), C2(H2), C10(H10)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              36594
_shelx_hkl_checksum              65773
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.965
_oxdiff_exptl_absorpt_empirical_full_min 0.657