Electrophilic Cyclization of Aryl Propargylic Alcohols: Synthesis of Dihalogenated 6,9-Dihydropyrido[1,2-a]indoles via a Cascade Iodocyclization.
Wang, Jia; Zhu, Hai-Tao; Chen, Si; Xia, Yu; Jin, Dong-Po; Qiu, Yi-Feng; Li, Ying-Xiu; Liang, Yong-Min; The Journal of organic chemistry 81 (2016) 10975–10986; doi:10.1021/acs.joc.6b02013

data_4037333
_publ_section_title
;
 Electrophilic Cyclization of Aryl Propargylic Alcohols: Synthesis of
 Dihalogenated 6,9-Dihydropyrido[1,2-a]indoles via a Cascade
 Iodocyclization.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10975
_journal_page_last               10986
_journal_paper_doi               10.1021/acs.joc.6b02013
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C25 H19 Br I N'
_chemical_formula_sum            'C25 H19 Br I N'
_chemical_formula_weight         540.22
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-02
_audit_creation_method
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Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.132(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.8314(6)
_cell_length_b                   12.0828(5)
_cell_length_c                   15.5269(6)
_cell_measurement_reflns_used    2379
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.7490
_cell_measurement_theta_min      3.6070
_cell_volume                     2032.06(16)
_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
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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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.870
_diffrn_measured_fraction_theta_max 0.870
_diffrn_measurement_details
;
  1 omega  -20.00    6.40   1.2000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.3041  -38.0000  120.0000 22

  2 omega  -39.00   48.60   1.2000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       20.7416  -77.0000  -90.0000 73

  3 omega   42.00   79.20   1.2000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       20.7416  178.0000 -150.0000 31

  4 omega  -11.00   88.60   1.2000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   19.0000   90.0000 83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0416427000
_diffrn_orient_matrix_UB_12      0.0439865000
_diffrn_orient_matrix_UB_13      -0.0084602000
_diffrn_orient_matrix_UB_21      0.0294250000
_diffrn_orient_matrix_UB_22      0.0097933000
_diffrn_orient_matrix_UB_23      -0.0400278000
_diffrn_orient_matrix_UB_31      -0.0410795000
_diffrn_orient_matrix_UB_32      -0.0376534000
_diffrn_orient_matrix_UB_33      -0.0202987000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            9864
_diffrn_reflns_theta_full        28.93
_diffrn_reflns_theta_max         28.93
_diffrn_reflns_theta_min         3.37
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.553
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61206
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.766
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.454
_refine_diff_density_min         -1.030
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         4671
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0809
_refine_ls_R_factor_gt           0.0454
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0358P)^2^+0.7217P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0877
_refine_ls_wR_factor_ref         0.1054
_reflns_number_gt                3101
_reflns_number_total             4671
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b02013_si_002.cif
_cod_data_source_block           wangjia0301
_cod_original_cell_volume        2032.06(17)
_cod_database_code               4037333
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C19(H19), C6(H6), C3(H3), C22(H22), C5(H5), C23(H23), C21(H21),
 C15(H15), C17(H17), C20(H20), C16(H16), C18(H18), C4(H4)
2.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_olex2_date_sample_data_collection 2016-03-01
_olex2_submission_special_instructions 'No special instructions were received'