Highly Stereoselective and Scalable Synthesis of trans-Fused Octahydrocyclohepta[b]pyrrol-4(1H)-ones via the Aza-Cope-Mannich Rearrangement in Racemic and Enantiopure Forms
Dmitry S. Belov; Evgeny R. Lukyanenko; Alexander V. Kurkin; Marina A. Yurovskaya; Journal of Organic Chemistry 77 (2012) 10125–10134; doi:10.1021/jo301762a

data_4027715
_publ_contact_author             'Dr Victor B. Rybakov'
_publ_contact_author_email       Rybakov20021@yandex.ru
_publ_section_title
;
 Highly Stereoselective and Scalable Synthesis of trans-Fused
 Octahydrocyclohepta[b]pyrrol-4(1H)-ones via the Aza-Cope-Mannich
 Rearrangement in Racemic and Enantiopure Forms
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              10125
_journal_page_last               10134
_journal_paper_doi               10.1021/jo301762a
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C22 H25 N O'
_chemical_formula_sum            'C22 H25 N O'
_chemical_formula_weight         319.43
_chemical_melting_point_gt       379.4
_chemical_melting_point_lt       379.9
_chemical_name_systematic
;
 (3RS,3aSR,8aRS)-1-benzyl-3-phenyloctahydrocyclohepta[b]pyrrol-4(1H)-one
;
_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           SHELXL97
_cell_angle_alpha                90.00
_cell_angle_beta                 115.90(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.469(4)
_cell_length_b                   5.6816(13)
_cell_length_c                   19.972(4)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      11.27
_cell_measurement_theta_min      9.92
_cell_volume                     1783.2(7)
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'scintillation LiI'
_diffrn_detector_dtime           1.195
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '\k--geometry diffractometer'
_diffrn_measurement_device_type  'Enraf Nonius CAD4'
_diffrn_measurement_method       'non--profiled \W--scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine--focus sealed tube'
_diffrn_radiation_type           AgK\a
_diffrn_radiation_wavelength     0.56085
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.1197
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            3896
_diffrn_reflns_theta_full        20.98
_diffrn_reflns_theta_max         20.98
_diffrn_reflns_theta_min         1.02
_diffrn_source                   'Enraf Nonius FR590'
_diffrn_standards_decay_%        1
_diffrn_standards_interval_time  60
_diffrn_standards_number         1
_exptl_absorpt_coefficient_mu    0.047
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       prism
_exptl_crystal_F_000             688
_exptl_crystal_preparation       'EtOH or hexane'
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.128
_refine_diff_density_min         -0.146
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.808
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3896
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.808
_refine_ls_R_factor_all          0.1908
_refine_ls_R_factor_gt           0.0570
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0470P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1015
_refine_ls_wR_factor_ref         0.1462
_reflns_number_gt                1310
_reflns_number_total             3896
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo301762a_si_001.cif
_cod_data_source_block           yur20
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4027715
_diffrn_standards_decay_corr_max 1.010
_diffrn_standards_decay_corr_min 0.980