On the Mechanism and Selectivity of the Combined C-H Activation/Cope Rearrangement
Jørn H. Hansen; Timothy M. Gregg; Stephanie R. Ovalles; Yajing Lian; Jochen Autschbach; Huw M. L. Davies; Journal of the American Chemical Society 133 (2011) 5076–5085; doi:10.1021/ja111408v

data_4105874
_publ_section_title
;
 On the Mechanism and Selectivity of the Combined C-H Activation/Cope
 Rearrangement
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5076
_journal_page_last               5085
_journal_paper_doi               10.1021/ja111408v
_journal_volume                  133
_journal_year                    2011
_chemical_formula_sum            'C16 H15 Br O2'
_chemical_formula_weight         319.19
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.9374(4)
_cell_length_b                   8.0353(5)
_cell_length_c                   28.7626(19)
_cell_measurement_reflns_used    74
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      27.00
_cell_measurement_theta_min      3.00
_cell_volume                     1372.23(16)
_computing_cell_refinement       SMART
_computing_data_collection       SMART
_computing_data_reduction        SAINT
_computing_molecular_graphics    XP
_computing_publication_material  XCIF
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(1)
_diffrn_measured_fraction_theta_full 0.941
_diffrn_measured_fraction_theta_max 0.941
_diffrn_measurement_device_type  'SMART CCD'
_diffrn_measurement_method       'omega oscillation'
_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  0.0612
_diffrn_reflns_av_sigmaI/netI    0.0738
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            8566
_diffrn_reflns_theta_full        28.75
_diffrn_reflns_theta_max         28.75
_diffrn_reflns_theta_min         2.63
_exptl_absorpt_coefficient_mu    2.990
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_description       needle
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.345
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.004(10)
_refine_ls_extinction_coef       0.0076(7)
_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   0.927
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     233
_refine_ls_number_reflns         3239
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.136
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0200P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0594
_refine_ls_wR_factor_ref         0.0629
_reflns_number_gt                2682
_reflns_number_total             3239
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja111408v_si_003.cif
_cod_data_source_block           a1
_cod_database_code               4105874