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_4027718
_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_absolute_configuration ad
_chemical_formula_moiety         '2(C23 H28 N O), C2 H6 O, 2(Br),H2 O'
_chemical_formula_sum            'C48 H64 Br2 N2 O4'
_chemical_formula_weight         892.81
_chemical_melting_point_gt       477.4
_chemical_melting_point_lt       477.7
_chemical_name_systematic
; 
 (3S,3aR,8aS)-3-phenyl-1-[(1R)-1-phenylethyl]octahydrocyclohepta 
[b]pyrrol-4(1H)-one 
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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           SHELXL97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.3917(8)
_cell_length_b                   20.6521(16)
_cell_length_c                   20.2498(17)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      9.98
_cell_measurement_theta_min      8.65
_cell_volume                     4345.8(6)
_computing_cell_refinement       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_collection       'CAD4 Express (Enraf Nonius, 1994)'
_computing_data_reduction        'XCAD4 (Harms & Wocadlo, 1995)'
_computing_molecular_graphics    'Ortep--3 (Farrugia, 1997)'
_computing_publication_material  'WinGX    (Farrugia, 1999)'
_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 0.922
_diffrn_measured_fraction_theta_max 0.922
_diffrn_measurement_device       '\k--geometry diffractometer'
_diffrn_measurement_device_type  'Enraf Nonius TurboCAD4'
_diffrn_measurement_method       'non--profiled \w--scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'fine--focus sealed tube'
_diffrn_radiation_type           AgK\a
_diffrn_radiation_wavelength     0.56085
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_sigmaI/netI    0.5588
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            8621
_diffrn_reflns_theta_full        20.91
_diffrn_reflns_theta_max         20.91
_diffrn_reflns_theta_min         1.11
_diffrn_source                   'Enraf Nonius FR590'
_diffrn_standards_decay_%        2
_diffrn_standards_interval_time  60
_diffrn_standards_number         1
_exptl_absorpt_coefficient_mu    1.030
_exptl_absorpt_correction_T_max  0.8138
_exptl_absorpt_correction_T_min  0.1044
_exptl_absorpt_correction_type   refdelf
_exptl_absorpt_process_details
;
 Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158--166.
;
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       Prism
_exptl_crystal_F_000             1872
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.349
_refine_diff_density_min         -0.666
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack, H. D. (1983). Acta Cryst. A39, 876--881. 
 The 3411 Friedel pairs were measured.
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.635
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         8621
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      0.634
_refine_ls_R_factor_all          0.3058
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0344P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0951
_refine_ls_wR_factor_ref         0.1633
_reflns_number_gt                1646
_reflns_number_total             8621
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo301762a_si_004.cif
_cod_data_source_block           yur22
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'x--ray' changed to 'x-ray' according
to the built-in table from CIF Core dictionary named 'cif_core.dic'
version 2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_database_code               4027718
_exptl_absorpt_factor_mur        0.206
_diffrn_standards_decay_corr_max 1.117
_diffrn_standards_decay_corr_min 0.880