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_7230944
_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         'C31 H25 N O3 S'
_chemical_formula_sum            'C31 H25 N O3 S'
_chemical_formula_weight         491.58
_chemical_name_systematic
(3R,9aS)-3,4-diphenyl-1-tosyl-9,9a-dihydro-1H-benzo[f]indol-2(3H)-one
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-08-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_audit_update_record
;
2017-08-17 deposited with the CCDC.
2018-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.550(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7246(4)
_cell_length_b                   12.2563(6)
_cell_length_c                   16.5665(7)
_cell_measurement_reflns_used    4594
_cell_measurement_temperature    99.97(10)
_cell_measurement_theta_max      65.5040
_cell_measurement_theta_min      3.8170
_cell_volume                     2354.15(17)
_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)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.926
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
  1 omega   81.00  165.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   45.0000  -60.0000 84

  2 omega  130.00  164.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000   60.0000 34

  3 omega   94.00  152.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000  120.0000 58

  4 omega   81.00  165.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   61.0000 -120.0000 84

  5 omega   33.00   58.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7547 -125.0000  -30.0000 25

  6 omega   47.00  121.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609 -125.0000 -120.0000 74

  7 omega   15.00   85.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -30.0000   90.0000 70

  8 omega  -48.00   35.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7547   37.0000   60.0000 83

  9 omega  -90.00   -2.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7547  125.0000   90.0000 88
;
_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      0.1128876000
_diffrn_orient_matrix_UB_12      0.0085890000
_diffrn_orient_matrix_UB_13      0.0605725000
_diffrn_orient_matrix_UB_21      0.0208535000
_diffrn_orient_matrix_UB_22      0.1151762000
_diffrn_orient_matrix_UB_23      -0.0322299000
_diffrn_orient_matrix_UB_31      -0.0667843000
_diffrn_orient_matrix_UB_32      0.0502018000
_diffrn_orient_matrix_UB_33      0.0641542000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.926
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8354
_diffrn_reflns_point_group_measured_fraction_full 0.926
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         64.995
_diffrn_reflns_theta_min         4.332
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.505
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75386
_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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.347
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         3942
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0430
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0573P)^2^+1.7449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1092
_refine_ls_wR_factor_ref         0.1149
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3487
_reflns_number_total             3942
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc01534a2.cif
_cod_data_source_block           exp_6994
_cod_depositor_comments
'Adding full bibliography for 7230942--7230944.cif.'
_cod_original_cell_volume        2354.15(18)
_cod_database_code               7230944
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.629
_reflns_odcompleteness_completeness 99.95
_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:
 C15(H15), C27(H27)
2.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C14(H14), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31),
  C32(H32), C34(H34)
2.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C)
;
_olex2_date_sample_data_collection 2015-08-24
_olex2_submission_special_instructions 'No special instructions were received'