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_4131502
_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'
_chemical_formula_sum            'C19 H22 N2 O4 S'
_chemical_formula_weight         374.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-12-05
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4720)
;
_cell_angle_alpha                90
_cell_angle_beta                 117.3470(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6878(6)
_cell_length_b                   23.1088(14)
_cell_length_c                   9.8408(6)
_cell_measurement_reflns_used    5236
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.433
_cell_measurement_theta_min      2.442
_cell_volume                     1956.9(2)
_computing_cell_refinement       'SAINT v8.32B (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.32B (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0530
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19309
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.315
_diffrn_reflns_theta_min         1.762
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.191
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6864
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0811 before and 0.0569 after correction.
The Ratio of minimum to maximum transmission is 0.9205.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_colour_primary    Colorless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       Block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.117
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         4709
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0430
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0421P)^2^+1.2079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0998
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3738
_reflns_number_total             4709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06007_si_003.cif
_cod_data_source_block           Hein03
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/ACS/depositions/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4131502
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2
 0.9 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C5(H5A,H5B), C11(H11A,H11B)
3.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C18(H18), C17(H17)
3.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C12(H12A,H12B,H12C)
3.e :
 C1(H1)
;
_shelx_res_checksum              67296
_shelx_hkl_checksum              53686