Bridgehead Lithiation-Substitution of Bridged Ketones, Lactones, Lactams, and Imides: Experimental Observations and Computational Insights
Christopher J. Hayes; Nigel S. Simpkins; Douglas T. Kirk; Lee Mitchell; Jerome Baudoux; Alexander J. Blake; Claire Wilson; Journal of the American Chemical Society 131 (2009) 8196–8210; doi:10.1021/ja9009875

data_4104526
_publ_section_title
;
 Bridgehead Lithiation-Substitution of Bridged Ketones, Lactones, Lactams,
 and Imides: Experimental Observations and Computational Insights
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8196
_journal_page_last               8210
_journal_paper_doi               10.1021/ja9009875
_journal_volume                  131
_journal_year                    2009
_chemical_formula_sum            'C16 H20 O2'
_chemical_formula_weight         244.32
_space_group_IT_number           1
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   'geometrically placed, OH delta-F'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                63.488(2)
_cell_angle_beta                 83.907(2)
_cell_angle_gamma                81.996(2)
_cell_formula_units_Z            4
_cell_length_a                   9.3099(13)
_cell_length_b                   12.519(2)
_cell_length_c                   12.858(2)
_cell_measurement_reflns_used    4456
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.5
_cell_measurement_theta_min      2.2
_cell_volume                     1326.3(3)
_computing_cell_refinement       'Bruker SAINT version 6.02a (Bruker, 2000)'
_computing_data_collection       'Bruker SMART version 5.054 (Bruker, 1998)'
_computing_data_reduction        'Bruker SAINT; Bruker SHELXTL (Bruker, 1997)'
_computing_publication_material  'SHELXL-97; PLATON (Spek, 2001)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.954
_diffrn_measured_fraction_theta_max 0.871
_diffrn_measurement_device_type  'Bruker SMART1000 CCD area detector'
_diffrn_measurement_method       omega
_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  0.082
_diffrn_reflns_av_sigmaI/netI    0.050
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11502
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         28.59
_diffrn_reflns_theta_min         1.77
_diffrn_standards_decay_%        none
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       tablet
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.57
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.57
_refine_diff_density_min         -0.32
_refine_diff_density_rms         0.05
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   'not reliably determined'
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    'riding model, OH rigid rotating group'
_refine_ls_matrix_type           full
_refine_ls_number_parameters     645
_refine_ls_number_reflns         5907
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0682
_refine_ls_R_factor_gt           0.0493
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0816P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1189
_refine_ls_wR_factor_ref         0.1285
_reflns_number_gt                4564
_reflns_number_total             5907
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9009875_si_002.cif
_cod_data_source_block           ocbzol
_cod_database_code               4104526