Reversal of Regioselectivity in Catalytic Arene-Ynamide Cyclization: Direct Synthesis of Valuable Azepino[4,5-b]indoles and β-Carbolines and DFT Calculations
Li, Long; Chen, Xiu-Mei; Wang, Ze-Shu; Zhou, Bo; Liu, Xin; Lu, Xin; Ye, Long-Wu; ACS Catalysis 7 (2017) 4004–; doi:10.1021/acscatal.7b01038

data_4516735
_publ_section_title
;
 Reversal of Regioselectivity in Catalytic Arene-Ynamide Cyclization:
 Direct Synthesis of Valuable Azepino[4,5-b]indoles and \b-Carbolines and
 DFT Calculations
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              4004
_journal_paper_doi               10.1021/acscatal.7b01038
_journal_volume                  7
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H24 N2 O2 S'
_chemical_formula_sum            'C21 H24 N2 O2 S'
_chemical_formula_weight         368.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.913(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.6188(3)
_cell_length_b                   16.8151(5)
_cell_length_c                   11.4121(3)
_cell_measurement_reflns_used    8697
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      74.8290
_cell_measurement_theta_min      3.8560
_cell_volume                     1843.42(9)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -117.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8797  -37.0000 -180.0000 102

  2 omega  -49.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8797   37.0000 -180.0000 84

  3 omega    1.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8797  -99.0000   90.0000 82

  4 omega    1.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8797  -99.0000   60.0000 82

  5 omega  100.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  113.0000  -20.0000 78

  6 omega   79.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067   61.0000   90.0000 99

  7 omega   36.00  140.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -61.0000 -150.0000 104

  8 omega   79.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067   30.0000  -90.0000 99

  9 omega   35.00   98.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -45.0000  120.0000 63

 10 omega   32.00   90.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -30.0000  -90.0000 58

 11 omega   32.00   90.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -30.0000  -30.0000 58

 12 omega   35.00  121.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067 -125.0000   30.0000 86

 13 omega -115.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8797  -57.0000  -60.0000 104

 14 omega  -49.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8797   37.0000  -30.0000 84

 15 omega -120.00   -7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8797  -77.0000   60.0000 113

 16 omega   79.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067   30.0000 -180.0000 99

 17 omega   26.00  109.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -94.0000   90.0000 83

 18 omega   32.00   90.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067  -30.0000   60.0000 58

 19 omega   82.00  129.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067   45.0000   60.0000 47

 20 omega   48.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.8067   15.0000   30.0000 130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71000
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.0640
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            15316
_diffrn_reflns_theta_full        23.79
_diffrn_reflns_theta_max         23.79
_diffrn_reflns_theta_min         1.78
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.194
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70486
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.096
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -1.53(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         5320
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0778
_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^)+(0.1280P)^2^+3.3922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2110
_refine_ls_wR_factor_ref         0.2152
_reflns_number_gt                5050
_reflns_number_total             5320
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs7b01038_si_003.cif
_cod_data_source_block           lr-20160805
_cod_original_cell_volume        1843.42(10)
_cod_database_code               4516735
_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), C11(H11), C36(H36), C32(H32)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C10(H10A,H10B), C31(H31A,H31B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C25(H25), C38(H38), C26(H26), C28(H28), C17(H17), C40(H40), C18(H18),
 C21(H21), C42(H42), C5(H5), C20(H20), C39(H39), C19(H19), C7(H7), C27(H27),
 C6(H6), C41(H41)
2.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C12(H12A,H12B,
 H12C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C)
;
_olex2_submission_special_instructions 'No special instructions were received'