Novel synthesis of azepine derivatives via copper-mediated cyclization of 2-aza-hepta-2,4-dien-6-ynyl anions. Intramolecular addition of organocopper centers to the C-C triple bond.
Lyaskovskyy, Volodymyr; Bergander, Klaus; Fröhlich, Roland; Würthwein, Ernst-Ulrich; Organic letters 9 (2007) 1049–1052; doi:10.1021/ol063081y

data_1505309
_publ_section_title
;
 Novel synthesis of azepine derivatives via copper-mediated cyclization of
 2-aza-hepta-2,4-dien-6-ynyl anions. Intramolecular addition of
 organocopper centers to the C-C triple bond.
;
_journal_issue                   6
_journal_name_full               'Organic letters'
_journal_page_first              1049
_journal_page_last               1052
_journal_paper_doi               10.1021/ol063081y
_journal_volume                  9
_journal_year                    2007
_chemical_formula_sum            'C26 H21 N3'
_chemical_formula_weight         375.46
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_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                 108.05(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   23.712(1)
_cell_length_b                   15.364(1)
_cell_length_c                   12.061(1)
_cell_measurement_reflns_used    3393
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.60
_cell_measurement_theta_min      0.88
_cell_volume                     4177.7(5)
_computing_cell_refinement       'Collect (Nonius B.V., 1998)'
_computing_data_collection       'Collect (Nonius B.V., 1998)'
_computing_data_reduction        'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'SCHAKAL (Keller, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Nonius KappaCCD APEXII'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.031
_diffrn_reflns_av_sigmaI/netI    0.0219
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13224
_diffrn_reflns_theta_full        66.60
_diffrn_reflns_theta_max         66.60
_diffrn_reflns_theta_min         3.92
_exptl_absorpt_coefficient_mu    0.550
_exptl_absorpt_correction_T_max  0.8980
_exptl_absorpt_correction_T_min  0.7900
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'Denzo (Otwinowski, Borek, Majewski & Minor, 2003)'
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       column
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.147
_refine_diff_density_rms         0.026
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3605
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0622P)^2^+1.7733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1169
_reflns_number_gt                3280
_reflns_number_total             3605
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol063081ysi20061220_092340.cif
_cod_data_source_block           wue3706
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               1505309