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_4114369
_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         '(C19 H28 N2 O4), (C H2 Cl2)0.33'
_chemical_formula_sum            'C19.33 H28.67 Cl0.67 N2 O4'
_chemical_formula_weight         376.74
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           148
_symmetry_cell_setting           rhombohedral
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_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                120.00
_cell_formula_units_Z            18
_cell_length_a                   40.0967(9)
_cell_length_b                   40.0967(9)
_cell_length_c                   6.2389(3)
_cell_measurement_reflns_used    5727
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.00
_cell_measurement_theta_min      2.69
_cell_volume                     8686.7(5)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker APEX'
_diffrn_measurement_method       '\w scan frames'
_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  0.0290
_diffrn_reflns_av_sigmaI/netI    0.0235
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            18427
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         2.69
_diffrn_standards_decay_%        -0.08
_diffrn_standards_number         172
_exptl_absorpt_coefficient_mu    0.178
_exptl_absorpt_correction_T_max  0.9737
_exptl_absorpt_correction_T_min  0.9418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, 2000'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_density_meas      0
_exptl_crystal_description       prism
_exptl_crystal_F_000             3636
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.405
_refine_diff_density_min         -0.178
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3799
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0466
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+10.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1172
_refine_ls_wR_factor_ref         0.1214
_reflns_number_gt                3254
_reflns_number_total             3799
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja0382361si20030830_011613_4.cif
_cod_data_source_block           compound_14a_
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               4114369