Synthesis of Tetrasubstituted Cyclopentadienes via Palladium-Catalyzed Reaction of (Z)-2-En-4-yn Acetates and N-Methyl Indoles
Mei-Jin Zhong; Xiang-Chuan Wang; Hai-Tao Zhu; Jie Hu; Lei Liu; Xue-Yuan Liu; Yong-Min Liang; Journal of Organic Chemistry 77 (2012) 10955–10961; doi:10.1021/jo3021055

data_4027770
_publ_contact_author_name
;
;
_publ_section_title
;
 Synthesis of Tetrasubstituted Cyclopentadienes via Palladium-Catalyzed
 Reaction of (Z)-2-En-4-yn Acetates and N-Methyl Indoles
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              10955
_journal_page_last               10961
_journal_paper_doi               10.1021/jo3021055
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C33 H26 N'
_chemical_formula_sum            'C33 H26 N'
_chemical_formula_weight         436.55
_chemical_name_systematic
;
 ? 
;
_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
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-11-01
_audit_creation_method
;
  Olex2 1.2
  (compiled 2012.05.09 svn.r2324, GUI svn.r4230)
;
_cell_angle_alpha                69.317(5)
_cell_angle_beta                 81.261(4)
_cell_angle_gamma                88.310(4)
_cell_formula_units_Z            2
_cell_length_a                   10.1773(5)
_cell_length_b                   10.6007(6)
_cell_length_c                   11.9185(6)
_cell_measurement_reflns_used    4406
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.5292
_cell_measurement_theta_min      4.0075
_cell_volume                     1188.60(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9629
_diffrn_measured_fraction_theta_max 0.9691
_diffrn_measurement_details
;
  1 omega  -78.00  -37.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -60.0000 41

  2 omega  -24.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   30.0000 64

  3 omega   43.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -120.0000 26

  4 omega  -78.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  120.0000 44

  5 omega  -43.00   10.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  109.0000   56.0000 53

  6 omega -133.00   16.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000    0.0000    0.0000 149

  7 omega  -73.00   -9.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000   57.0000   30.0000 64

  8 omega   23.00  112.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000 -125.0000  -30.0000 89

  9 omega -107.00  -79.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000 -111.0000 -150.0000 28

 10 omega  -90.00    4.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000   63.0000 -120.0000 94

 11 omega  -89.00  -18.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000   63.0000  120.0000 71

 12 omega  -39.00   -8.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000   38.0000 -150.0000 31

 13 omega  -60.00  -31.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000   50.0000 -180.0000 29

 14 omega   87.00  123.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -77.0000 -180.0000 36

 15 omega   46.00   72.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -77.0000 -180.0000 26

 16 omega  130.00  166.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   50.0000  -90.0000 36

 17 omega   61.00  115.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000   30.0000 54

 18 omega   79.00  140.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -63.0000 -180.0000 61

 19 omega   97.00  126.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   50.0000  -90.0000 29

 20 omega   46.00   95.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -50.0000    0.0000 49

 21 omega  112.00  171.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  111.0000  -90.0000 59

 22 omega   91.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000   90.0000 25

 23 omega   50.00   79.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000  150.0000 29

 24 omega   44.00   94.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -91.0000  -30.0000 50

 25 omega  107.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  111.0000  -30.0000 68

 26 omega   43.00   85.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000    0.0000 42

 27 omega   43.00   68.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000   60.0000 25

 28 omega   52.00   78.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -77.0000  -30.0000 26

 29 omega   77.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000 -120.0000 39

 30 omega  129.00  177.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   50.0000 -120.0000 48

 31 omega   60.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000  150.0000 49

 32 omega   50.00   81.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -38.0000   60.0000 31

 33 omega   91.00  117.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   63.0000   60.0000 26

 34 omega   52.00   87.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -50.0000 -180.0000 35

 35 omega   44.00   73.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -91.0000 -180.0000 29

 36 omega   97.00  174.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   38.0000  -30.0000 77

 37 omega  144.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   63.0000   60.0000 34

 38 omega   66.00   92.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  178.0000   60.0000 26

 39 omega   49.00   80.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -63.0000    0.0000 31

 40 omega   93.00  148.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -77.0000  -30.0000 55

 41 omega   96.00  172.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000   50.0000   30.0000 76

 42 omega   81.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000 -111.0000 -150.0000 35

 43 omega   44.00   70.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -25.0000  -60.0000 26

 44 omega   59.00   90.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -38.0000  -90.0000 31

 45 omega  105.00  130.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -77.0000    0.0000 25

 46 omega  103.00  129.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  -91.0000 -150.0000 26

 47 omega  108.00  148.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      116.0000  111.0000  -60.0000 40
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0494312000
_diffrn_orient_matrix_UB_12      0.0795891000
_diffrn_orient_matrix_UB_13      -0.1349805000
_diffrn_orient_matrix_UB_21      -0.0370600000
_diffrn_orient_matrix_UB_22      0.1329637000
_diffrn_orient_matrix_UB_23      0.0205459000
_diffrn_orient_matrix_UB_31      0.1401936000
_diffrn_orient_matrix_UB_32      0.0115261000
_diffrn_orient_matrix_UB_33      0.0299101000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0211
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9794
_diffrn_reflns_theta_full        72.68
_diffrn_reflns_theta_max         72.68
_diffrn_reflns_theta_min         4.01
_diffrn_source                   'SuperNova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    0.531
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.220
_exptl_crystal_description       block
_exptl_crystal_F_000             462
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.715
_refine_diff_density_min         -0.629
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         4673
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0711P)^2^+0.4992P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1317
_refine_ls_wR_factor_ref         0.1386
_reflns_number_gt                4123
_reflns_number_total             4673
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo3021055_si_002.cif
_cod_data_source_block           zhongmeijin1031
_cod_original_cell_volume        1188.59(11)
_cod_database_code               4027770
_reflns_odcompleteness_completeness 96.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H5 of C5, H8 of C8, H12 of C12, H2 of C2, H3 of C3, H4 of C4, H30 of C30,
  H27 of C27, H31 of C31, H25 of C25, H28 of C28, H15 of C15, H16 of C16, H17
  of C17, H18 of C18, H19 of C19, H21 of C21, H22 of C22, H23 of C23, H24 of C24
 At 1.5 times of:
  {H32A,H32B,H32C} of C32, {H33A,H33B,H33C} of C33
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C12(H12), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
  C27(H27), C28(H28), C30(H30), C31(H31)
2.b Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;