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_4104528
_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_moiety         'C17 H23 N O2 Si'
_chemical_formula_sum            'C17 H23 N O2 Si'
_chemical_formula_weight         301.45
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_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                 102.430(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.0710(12)
_cell_length_b                   6.1798(7)
_cell_length_c                   24.568(3)
_cell_measurement_reflns_used    15216
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      29.3
_cell_measurement_theta_min      3.55
_cell_volume                     1641.5(3)
_computing_cell_refinement       'SAINT version 5.00 (Bruker, 1996)'
_computing_data_collection       'SMART version 5.054 (Bruker, 1998)'
_computing_data_reduction        'SAINT; SHELXTL version 5.1 (Bruker, 1997)'
_computing_molecular_graphics    'SHELXTL/PC version 5.10)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker SMART CCD area detector'
_diffrn_measurement_method       omega
_diffrn_radiation_monochromator  germanium
_diffrn_radiation_source         'Daresbury Laboratory Station 9.8'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.68920
_diffrn_reflns_av_R_equivalents  0.043
_diffrn_reflns_av_sigmaI/netI    0.073
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            14107
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         1.83
_diffrn_standards_decay_%        none
_exptl_absorpt_coefficient_mu    0.147
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.220
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.388
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.20(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.935
_refine_ls_hydrogen_treatment    'riding model'
_refine_ls_matrix_type           full
_refine_ls_number_parameters     380
_refine_ls_number_reflns         6889
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.935
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0670P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1191
_reflns_number_gt                5573
_reflns_number_total             6889
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9009875_si_004.cif
_cod_data_source_block           cximph
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_hydrogens' value 'placed geometrically' was
changed to 'geom'.

Automatic conversion script
Id: cif_fix_values 6452 2018-10-05 10:23:21Z andrius 
;
_cod_database_code               4104528