Experimental and Computational Studies on the [3,3]- and [3,5]-Sigmatropic Rearrangements of Acetoxycyclohexadienones: A Non-ionic Mechanism for Acyl Migration
Shikha Sharma; Trideep Rajale; David B. Cordes; Fernando Hung-Low; David M. Birney; Journal of the American Chemical Society 135 (2013) 14438–14447; doi:10.1021/ja4077364

data_4120860
_publ_contact_author_address
;Department of Chemistry and Biochemistry
Texas Tech University
Lubbock, TX 79409
USA
;
_publ_contact_author_email       David.Birney@ttu.edu
_publ_contact_author_fax         +1-806-742-1289
_publ_contact_author_name        'David M. Birney'
_publ_contact_author_phone       +1-806-742-3063
_publ_section_title
;
 Experimental and Computational Studies on the [3,3]- and
 [3,5]-Sigmatropic Rearrangements of Acetoxycyclohexadienones: A Non-ionic
 Mechanism for Acyl Migration
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14438
_journal_page_last               14447
_journal_paper_doi               10.1021/ja4077364
_journal_volume                  135
_journal_year                    2013
_chemical_formula_sum            'C11 H12 O5'
_chemical_formula_weight         224.21
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.00
_cell_angle_beta                 108.7940(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.5871(8)
_cell_length_b                   11.4756(11)
_cell_length_c                   11.6880(11)
_cell_measurement_reflns_used    103
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      25.68
_cell_measurement_theta_min      1.58
_cell_volume                     1090.35(18)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_sigmaI/netI    0.0185
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10196
_diffrn_reflns_theta_full        25.67
_diffrn_reflns_theta_max         25.67
_diffrn_reflns_theta_min         2.56
_exptl_absorpt_coefficient_mu    0.109
_exptl_absorpt_correction_T_max  0.9819
_exptl_absorpt_correction_T_min  0.9730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker SADABS'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       Block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         2071
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0391P)^2^+0.3684P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0808
_refine_ls_wR_factor_ref         0.0867
_reflns_number_gt                1735
_reflns_number_total             2071
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja4077364_si_001_3.cif
_cod_data_source_block           9
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4120860