Stereocontrolled Synthesis of Substituted Chiral Piperidines via One-Pot Asymmetric 6π-Azaelectrocyclization: Asymmetric Syntheses of (-)-Dendroprimine, (+)-7-Epidendroprimine, (+)-5-Epidendroprimine, and (+)-5,7-Epidendroprimine
Toyoharu Kobayashi; Futoshi Hasegawa; Yoshikatsu Hirose; Katsunori Tanaka; Hajime Mori; Shigeo Katsumura; Journal of Organic Chemistry 77 (2012) 1812–1832; doi:10.1021/jo202350z

data_4026965
_publ_section_title
;
 Stereocontrolled Synthesis of Substituted Chiral Piperidines via One-Pot
 Asymmetric 6\p-Azaelectrocyclization: Asymmetric Syntheses of
 (-)-Dendroprimine, (+)-7-Epidendroprimine, (+)-5-Epidendroprimine, and
 (+)-5,7-Epidendroprimine
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              1812
_journal_page_last               1832
_journal_paper_doi               10.1021/jo202350z
_journal_volume                  77
_journal_year                    2012
_chemical_compound_source        'Local laboratory'
_chemical_formula_moiety         'C29 H45 N O4 Si '
_chemical_formula_sum            'C29 H45 N O4 Si'
_chemical_formula_weight         499.768
_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
_cell_angle_alpha                90.00
_cell_angle_beta                 101.43(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   15.255(3)
_cell_length_b                   10.757(3)
_cell_length_c                   9.418(2)
_cell_measurement_reflns_used    26
_cell_measurement_temperature    298
_cell_measurement_theta_max      29.9
_cell_measurement_theta_min      27.0
_cell_volume                     1514.8(6)
_computing_cell_refinement       'MXC(MAC Science)'
_computing_data_collection       'MXC(MAC Science)'
_computing_data_reduction        'maXus (Mackay et al., 1999)'
_computing_molecular_graphics    'Ortep (Johnson, 1976)'
_computing_publication_material  'maXus(Mackay et al., 1999)'
_computing_structure_refinement  'maXus(Mackay et al., 1999)'
_diffrn_measurement_device       'Mac Science MXC18'
_diffrn_measurement_method       '\q \w scans'
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      -0.00745
_diffrn_orient_matrix_UB_12      -0.09235
_diffrn_orient_matrix_UB_13      -0.00520
_diffrn_orient_matrix_UB_21      0.05736
_diffrn_orient_matrix_UB_22      -0.00762
_diffrn_orient_matrix_UB_23      -0.03547
_diffrn_orient_matrix_UB_31      0.03357
_diffrn_orient_matrix_UB_32      -0.00739
_diffrn_orient_matrix_UB_33      0.10222
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           ' CuK\a'
_diffrn_radiation_wavelength_id  all
_diffrn_reflns_av_R_equivalents  0.092
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       0
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            2176
_diffrn_reflns_theta_full        54.96
_diffrn_reflns_theta_max         54.96
_diffrn_reflns_theta_min         2.96
_diffrn_standards_number         2176
_exptl_absorpt_coefficient_mu    0.92
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.096
_exptl_crystal_description       Cube
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.21
_refine_diff_density_min         -0.78
_refine_diff_density_rms         0.10
_refine_ls_abs_structure_details
;
;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_all   27.826
_refine_ls_goodness_of_fit_gt    10.580
_refine_ls_goodness_of_fit_ref   10.580
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_constraints    45
_refine_ls_number_parameters     316
_refine_ls_number_reflns         1966
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.147
_refine_ls_R_factor_gt           0.143
_refine_ls_shift/su_max          3.675
_refine_ls_shift/su_mean         0.653
_refine_ls_structure_factor_coef F^2^
_refine_ls_weighting_details
; 
 w = 1 / ( s^2^(Fo^2^) + 0.00010 * Fo^2^)
;
_refine_ls_weighting_scheme      sigma
_refine_ls_wR_factor_all         0.273
_refine_ls_wR_factor_gt          0.273
_refine_ls_wR_factor_ref         0.273
_reflns_d_resolution_high        0.69
_reflns_d_resolution_low         2.73
_reflns_limit_h_max              16
_reflns_limit_h_min              0
_reflns_limit_k_max              11
_reflns_limit_k_min              0
_reflns_limit_l_max              9
_reflns_limit_l_min              -10
_reflns_number_gt                1966
_reflns_number_total             2036
_reflns_threshold_expression     'I> 3.00 sigma(I)'
_cod_data_source_file            jo202350z_si_001.cif
_cod_data_source_block           global
_cod_depositor_comments          'Adding Fobs data.'
_cod_original_cell_volume        1514.9(6)
_cod_original_sg_symbol_H-M      'P 21'
_cod_original_formula_sum        'C29 H45 N O4 Si '
_cod_database_code               4026965
_cod_database_fobs_code          4026965