Enantiocontrolled Synthesis of 2,6-Disubstituted Piperidines by Desymmetrization of meso-η-(3,4,5)-Dihydropyridinylmolybdenum Complexes. Application to the Total Synthesis of (-)-Dihydropinidine and (-)-Andrachcinidine
Chutian Shu; Lanny S. Liebeskind; Journal of the American Chemical Society 125 (2003) 2878–2879; doi:10.1021/ja029537y

data_4113550
_publ_section_title
;
 Enantiocontrolled Synthesis of 2,6-Disubstituted Piperidines by
 Desymmetrization of meso-\h-(3,4,5)-Dihydropyridinylmolybdenum Complexes.
 Application to the Total Synthesis of (-)-Dihydropinidine and
 (-)-Andrachcinidine
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2878
_journal_page_last               2879
_journal_paper_doi               10.1021/ja029537y
_journal_volume                  125
_journal_year                    2003
_chemical_formula_sum            'C31 H45 N O5'
_chemical_formula_weight         511.68
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.3482(5)
_cell_length_b                   8.6750(5)
_cell_length_c                   40.331(2)
_cell_measurement_reflns_used    8330
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.33
_cell_measurement_theta_min      2.40
_cell_volume                     2920.8(3)
_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 0.963
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_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  0.0332
_diffrn_reflns_av_sigmaI/netI    0.0307
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       60
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            51997
_diffrn_reflns_theta_full        33.09
_diffrn_reflns_theta_max         33.09
_diffrn_reflns_theta_min         2.02
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.941454
_exptl_absorpt_correction_type   'multi-scan SADABS and face-indexing'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.164
_exptl_crystal_density_meas      0
_exptl_crystal_description       Rod
_exptl_crystal_F_000             1112
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.6(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     340
_refine_ls_number_reflns         10477
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0487
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0718P)^2^+0.1996P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1176
_refine_ls_wR_factor_ref         0.1202
_reflns_number_gt                9624
_reflns_number_total             10477
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja029537ysi20030123_053555.cif
_cod_data_source_block           cs462fs
_cod_database_code               4113550