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_4027717
_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 rmad
_chemical_compound_source        'Synthesis as described'
_chemical_formula_moiety         'C22 H26 N O, Br '
_chemical_formula_sum            'C22 H26 Br N O'
_chemical_formula_weight         400.34
_chemical_melting_point_gt       531.9
_chemical_melting_point_lt       532.6
_chemical_name_systematic
;
 (1S,2R)-2-{[(1R)-1-phenylethyl]amino}-1-(phenylethynyl)cyclohexanol
 hydrobromide
;
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL97
_cell_angle_alpha                90.00
_cell_angle_beta                 115.00(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   9.8448(11)
_cell_length_b                   10.7110(18)
_cell_length_c                   10.5116(17)
_cell_measurement_reflns_used    25
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      36.43
_cell_measurement_theta_min      32.68
_cell_volume                     1004.6(3)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'scintillation LiI'
_diffrn_detector_dtime           1.195
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_sigmaI/netI    0.0320
_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       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4606
_diffrn_reflns_theta_full        74.75
_diffrn_reflns_theta_max         74.75
_diffrn_reflns_theta_min         4.64
_diffrn_source                   'Enraf Nonius FR590'
_diffrn_standards_decay_%        3
_diffrn_standards_interval_time  120
_diffrn_standards_number         1
_exptl_absorpt_coefficient_mu    2.841
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       Prism
_exptl_crystal_F_000             416
_exptl_crystal_preparation       'EtOH/Et~2~O : 10/1'
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack, H. D. (1983). Acta Cryst. A39, 876-881.
 The 1964 Friedel pairs were measured.
;
_refine_ls_abs_structure_Flack   -0.062(19)
_refine_ls_extinction_coef       0.0070(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         4142
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0348P)^2^+0.3565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0863
_reflns_number_gt                3810
_reflns_number_total             4142
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            jo301762a_si_003.cif
_cod_data_source_block           yur2
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_absolute_configuration' value 'Rmad' changed to 'rmad'
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_original_sg_symbol_H-M      'P 21'
_cod_database_code               4027717
_diffrn_standards_decay_corr_max 1.053
_diffrn_standards_decay_corr_min 0.986