Reaction of Silyldihalomethyllithiums with Nitriles: Formation of α-Keto Acylsilanes via Azirines and 1,3-Rearrangement of Silyl Group from C to N
Kazunari Yagi; Takayuki Tsuritani; Kazuaki Takami; Hiroshi Shinokubo; Koichiro Oshima; Journal of the American Chemical Society 126 (2004) 8618–8619; doi:10.1021/ja047708o

data_4112751
_publ_contact_author
; 
Prof Dr. Hiroshi Shinokubo 
 Department of Chemistry 
 Graduate School of Science 
 Kyoto University 
 Kyoto 606-8502 
 Japan 
;
_publ_contact_author_email       hshino@kuchem.kyoto-u.ac.jp
_publ_section_title
;
 Reaction of Silyldihalomethyllithiums with Nitriles: Formation of \a-Keto
 Acylsilanes via Azirines and 1,3-Rearrangement of Silyl Group from C to N
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8618
_journal_page_last               8619
_journal_paper_doi               10.1021/ja047708o
_journal_volume                  126
_journal_year                    2004
_chemical_formula_sum            'C21 H27 N O Si'
_chemical_formula_weight         337.53
_chemical_name_systematic
; 
 2-(tert-Butyldimethylsilyl)-3-(4-methoxyphenyl)-2-phenyl-2H-azirine 
;
_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
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 92.0980(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.1359(8)
_cell_length_b                   14.2633(11)
_cell_length_c                   12.4072(9)
_cell_measurement_temperature    293(2)
_cell_volume                     1969.4(3)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.922
_diffrn_measured_fraction_theta_max 0.922
_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  0.0387
_diffrn_reflns_av_sigmaI/netI    0.0351
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            11789
_diffrn_reflns_theta_full        28.21
_diffrn_reflns_theta_max         28.21
_diffrn_reflns_theta_min         2.18
_exptl_absorpt_coefficient_mu    0.126
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.234
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.669
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         4476
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.669
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0541
_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^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1581
_refine_ls_wR_factor_ref         0.1782
_reflns_number_gt                3190
_reflns_number_total             4476
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja047708osi20040421_011419.cif
_cod_data_source_block           ky3x07
_cod_database_code               4112751