Transition-metal-free oxidative cyclization of N-propargyl ynamides: stereospecific construction of linear polycyclic N-heterocycles
Wang, Cai-Ming; Qi, Lin-Jun; Sun, Qing; Zhou, Bo; Zhang, Zhi-Xin; Shi, Zai-Fa; Lin, Shui-Chao; Lu, Xin; Gong, Lei; Ye, Long-Wu; Green Chemistry 20 (2018) 3271–; doi:10.1039/C8GC01534A

data_7230942
_publ_section_title
;
 Transition-metal-free oxidative cyclization of N-propargyl ynamides:
 stereospecific construction of linear polycyclic N-heterocycles
;
_journal_issue                   14
_journal_name_full               'Green Chemistry'
_journal_page_first              3271
_journal_paper_doi               10.1039/C8GC01534A
_journal_volume                  20
_journal_year                    2018
_chemical_formula_moiety         'C40 H31 Br N2 O5 S2'
_chemical_formula_sum            'C42 H36 Br Cl2 N2 O5.5 S2'
_chemical_formula_weight         871.66
_chemical_name_systematic
(3S,10aS)-1-((4-bromophenyl)sulfonyl)-7-methyl-3,4-diphenyl-9-tosyl-3,9,10,10a-tetrahydropyrrolo[2,3-b]carbazol-2(1H)-one
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-08-17 deposited with the CCDC.
2018-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                110.962(5)
_cell_angle_beta                 96.295(4)
_cell_angle_gamma                91.276(4)
_cell_formula_units_Z            2
_cell_length_a                   10.1352(5)
_cell_length_b                   13.2429(7)
_cell_length_c                   16.5954(8)
_cell_measurement_reflns_used    4686
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      64.0020
_cell_measurement_theta_min      3.6830
_cell_volume                     2062.93(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.948
_diffrn_measured_fraction_theta_max 0.948
_diffrn_measurement_details
;
  1 omega -115.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -57.0000  -90.0000 104

  2 omega -119.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -77.0000 -120.0000 112

  3 omega -119.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -77.0000   30.0000 112

  4 omega -119.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -77.0000  -30.0000 112

  5 omega -119.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -77.0000 -150.0000 112

  6 omega  -96.00   -2.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  125.0000  -30.0000 94

  7 omega -119.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -77.0000  120.0000 112

  8 omega   23.00   98.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5672 -125.0000 -120.0000 75

  9 omega   59.00  167.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   69.0000  -41.8642 108

 10 omega    7.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -94.0000  120.0000 102

 11 omega    7.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -94.0000 -120.0000 102

 12 omega   58.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   77.0000 -120.0000 112

 13 omega   58.00  169.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   75.0000   39.2826 111

 14 omega   58.00  169.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   76.0000 -159.6954 111

 15 omega   94.00  166.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000   60.0000 72

 16 omega   58.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   77.0000 -180.0000 112

 17 omega   58.00  169.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   74.0000   76.4023 111

 18 omega   58.00   83.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   77.0000  -90.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1483619000
_diffrn_orient_matrix_UB_12      -0.0096793000
_diffrn_orient_matrix_UB_13      0.0263621000
_diffrn_orient_matrix_UB_21      -0.0321036000
_diffrn_orient_matrix_UB_22      -0.0023015000
_diffrn_orient_matrix_UB_23      0.0879633000
_diffrn_orient_matrix_UB_31      -0.0211318000
_diffrn_orient_matrix_UB_32      -0.1244531000
_diffrn_orient_matrix_UB_33      -0.0401158000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2000
_diffrn_reflns_av_unetI/netI     0.1484
_diffrn_reflns_Laue_measured_fraction_full 0.948
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19767
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        61.160
_diffrn_reflns_theta_max         61.160
_diffrn_reflns_theta_min         3.582
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.882
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38907
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_F_000             894
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_refine_diff_density_max         4.872
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.281
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.981
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         6019
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.981
_refine_ls_R_factor_all          0.2899
_refine_ls_R_factor_gt           0.1978
_refine_ls_shift/su_max          0.251
_refine_ls_shift/su_mean         0.035
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1504P)^2^+3.5839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4901
_refine_ls_wR_factor_ref         0.5161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3528
_reflns_number_total             6019
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01534a2.cif
_cod_data_source_block           wcm-170401
_cod_depositor_comments
'Adding full bibliography for 7230942--7230944.cif.'
_cod_original_formula_sum        'C42 H36 Br Cl2 N2 O5.50 S2'
_cod_database_code               7230942
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 94.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_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.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C00P(H00A,H00B)
2.c Aromatic/amide H refined with riding coordinates:
 C00N(H00N), C00O(H00O), C00R(H00R), C00S(H00S), C00T(H00T), C00V(H00V),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C012(H012), C013(H013),
 C015(H015), C018(H018), C019(H019), C01A(H01A), C01B(H01B), C01C(H01C),
 C01D(H01D), C01F(H01H), C1AA(H1AA)
2.d Idealised Me refined as rotating group:
 C01E(H01E,H01F,H01G), C01G(H01I,H01J,H01K)
;
_olex2_submission_special_instructions 'No special instructions were received'