Mechanism of a No-Metal-Added Heterocycloisomerization of Alkynylcyclopropylhydrazones: Synthesis of Cycloheptane-Fused Aminopyrroles Facilitated by Copper Salts at Trace Loadings.
Wilkerson-Hill, Sidney M; Yu, Diana; Painter, Phillip P.; Fisher, Ethan L.; Tantillo, Dean J.; Sarpong, Richmond; Hein, Jason E.; Journal of the American Chemical Society 139 (2017) 10569–10577; doi:10.1021/jacs.7b06007

data_4131503
_publ_section_title
;
 Mechanism of a No-Metal-Added Heterocycloisomerization of
 Alkynylcyclopropylhydrazones: Synthesis of Cycloheptane-Fused
 Aminopyrroles Facilitated by Copper Salts at Trace Loadings.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10569
_journal_page_last               10577
_journal_paper_doi               10.1021/jacs.7b06007
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C19 H22 N2 O4 S, 0.34(C6 H6)'
_chemical_formula_sum            'C21.05 H24.05 N2 O4 S'
_chemical_formula_weight         401.17
_chemical_name_common            SMHVI-hydrazone
_chemical_name_systematic
; 
 sarpong66 
;
_space_group.centring_type       C-centered
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 97.743(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.1144(10)
_cell_length_b                   17.0847(5)
_cell_length_c                   10.0476(3)
_cell_measurement_reflns_used    9905
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.54
_cell_measurement_theta_min      3.03
_cell_volume                     4782.1(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    ORTEP-32
_computing_publication_material  WinGX
_computing_structure_refinement  SHELXL-2013
_computing_structure_solution    SHELXT
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_refln_scan_rate          10
_diffrn_refln_scan_width         1.0
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            30737
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         68.602
_diffrn_reflns_theta_min         3.034
_diffrn_source                   'microfocus rotating anode'
_exptl_absorpt_coefficient_mu    1.411
_exptl_absorpt_correction_T_max  0.929
_exptl_absorpt_correction_T_min  0.853
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.114
_exptl_crystal_description       blade
_exptl_crystal_F_000             1698.9
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.024
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         4366
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0539
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1082P)^2^+5.7956P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1644
_refine_ls_wR_factor_ref         0.1695
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3796
_reflns_number_total             4366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06007_si_002.cif
_cod_data_source_block           sarpong66
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               4131503
_shelx_estimated_absorpt_t_min   0.895
_shelx_estimated_absorpt_t_max   0.972
_shelxl_version_number           2013-4
_shelx_res_checksum              24728
_shelx_hkl_checksum              58570