Unusual Tethering Effects in the Schmidt Reaction of Hydroxyalkyl Azides with Ketones: Cation-π and Steric Stabilization of a Pseudoaxial Phenyl Group
Christopher E. Katz; Jeffrey Aubé; Journal of the American Chemical Society 125 (2003) 13948–13949; doi:10.1021/ja0382361

data_4114370
_publ_contact_author
; 
   Prof. Jeffrey Aub\'e 
   Department of Medicinal Chemistry 
   University of Kansas 
   Malott Hall, Room 4070 
   1251 Wescoe Hall Dr. 
   Lawrence, KS  66045-7582  USA 
;
_publ_contact_author_email       jaube@ku.edu
_publ_contact_author_fax         1(785)8645326
_publ_contact_author_phone       1(785)8644496
_publ_section_title
;
 Unusual Tethering Effects in the Schmidt Reaction of Hydroxyalkyl Azides
 with Ketones: Cation-\p and Steric Stabilization of a Pseudoaxial Phenyl
 Group
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13948
_journal_page_last               13949
_journal_paper_doi               10.1021/ja0382361
_journal_volume                  125
_journal_year                    2003
_chemical_formula_moiety         'C20 H31 N O2'
_chemical_formula_sum            'C20 H31 N O2'
_chemical_formula_weight         317.46
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 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                 97.40(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.859(4)
_cell_length_b                   12.026(4)
_cell_length_c                   13.269(3)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      42.16
_cell_measurement_theta_min      20.41
_cell_volume                     1876.6(10)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      298(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku AFC5R'
_diffrn_measurement_method       '\q-2\q scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_sigmaI/netI    0.0335
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            2931
_diffrn_reflns_theta_full        60.00
_diffrn_reflns_theta_max         60.08
_diffrn_reflns_theta_min         3.76
_diffrn_standards_decay_%        -1.83
_diffrn_standards_interval_count 150
_diffrn_standards_number         3
_exptl_absorpt_coefficient_mu    0.554
_exptl_absorpt_correction_T_max  0.8973
_exptl_absorpt_correction_T_min  0.8739
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            prism
_exptl_crystal_density_diffrn    1.124
_exptl_crystal_description       colorless
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.184
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0042(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   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2782
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0714
_refine_ls_R_factor_gt           0.0526
_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^)+(0.0908P)^2^+0.4080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1485
_refine_ls_wR_factor_ref         0.1605
_reflns_number_gt                2125
_reflns_number_total             2782
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0382361si20030830_011613_5.cif
_cod_data_source_block           compound_15b_
_cod_database_code               4114370