Effect of Intramolecular Paternò-Büchi Reaction on the Thermodynamics and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional Polycycles
Roman A. Valiulin; Donald G. Dressen; Jennifer R. Riggs; Faven M. Habte; Andrei G. Kutateladze; Journal of Organic Chemistry 74 (2009) 3484–3490; doi:10.1021/jo9003822

data_4024513
_publ_section_title
;
Effect of Intramolecular Patern\`o-B\"uchi Reaction on the Thermodynamics
and Kinetics of Nearly Degenerate [3,3]-Sigmatropic Shift in Fluxional
Polycycles
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              3484
_journal_page_last               3490
_journal_paper_doi               10.1021/jo9003822
_journal_volume                  74
_journal_year                    2009
_chemical_formula_sum            'C32 H28 O2'
_chemical_formula_weight         444.54
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                106.6850(10)
_cell_angle_beta                 91.7060(10)
_cell_angle_gamma                91.060(2)
_cell_formula_units_Z            2
_cell_length_a                   6.7012(4)
_cell_length_b                   10.9484(6)
_cell_length_c                   16.1361(9)
_cell_measurement_reflns_used    10186
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.0
_cell_volume                     1133.07(11)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      223(2)
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Rigaku SCXmini'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0225
_diffrn_reflns_av_sigmaI/netI    0.0291
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11912
_diffrn_reflns_theta_full        27.47
_diffrn_reflns_theta_max         27.47
_diffrn_reflns_theta_min         3.04
_exptl_absorpt_coefficient_mu    0.080
_exptl_absorpt_correction_T_max  0.9921
_exptl_absorpt_correction_T_min  0.9689
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.0086(17)
_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   1.016
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5162
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0477P)^2^+0.5157P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1251
_reflns_number_gt                4003
_reflns_number_total             5162
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9003822_si_002.cif
_cod_data_source_block           shelxl
_cod_database_code               4024513