Base-Promoted N-Pyridylation of Heteroarenes Using N-Propargyl Enaminones as Equivalents of Pyridine Scaffolds.
Cheng, Guolin; Weng, Yunxiang; Yang, Xifa; Cui, Xiuling; Organic letters 17 (2015) 3790–3793; doi:10.1021/acs.orglett.5b01733

data_1529884
_publ_section_title
;
 Base-Promoted N-Pyridylation of Heteroarenes Using N-Propargyl Enaminones
 as Equivalents of Pyridine Scaffolds.
;
_journal_issue                   15
_journal_name_full               'Organic letters'
_journal_page_first              3790
_journal_page_last               3793
_journal_paper_doi               10.1021/acs.orglett.5b01733
_journal_volume                  17
_journal_year                    2015
_chemical_formula_moiety         'C26 H20 N2'
_chemical_formula_sum            'C26 H20 N2'
_chemical_formula_weight         360.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-13
_audit_creation_method
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Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
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_cell_angle_alpha                90
_cell_angle_beta                 110.777(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.3348(7)
_cell_length_b                   10.6730(2)
_cell_length_c                   18.3612(6)
_cell_measurement_reflns_used    2856
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      71.7850
_cell_measurement_theta_min      3.9650
_cell_volume                     3909.1(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega   41.00   68.00   1.0000    1.0600
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -150.0000 27

  2 omega  -87.00  -29.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  125.0000  -90.0000 58

  3 omega -119.00  -72.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -60.0000 47

  4 omega  -37.00   28.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  -30.0000 65

  5 omega -110.00  -50.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000    0.0000 60

  6 omega   -6.00   79.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -37.0000  150.0000 85

  7 omega   39.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -120.0000 49

  8 omega   41.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -180.0000 47

  9 omega   40.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -30.0000 48

 10 omega   94.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000    0.0000 82

 11 omega   43.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -150.0000 26

 12 omega   41.00   72.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   30.0000 31

 13 omega   45.00   93.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   90.0000 48

 14 omega   67.00   94.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000   60.0000 27

 15 omega   46.00  108.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  120.0000 62

 16 omega   46.00   90.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   30.0000 44

 17 omega  -70.00   30.00   1.0000    1.0600
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000   90.0000 100

 18 omega   30.00  128.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   37.0000 -150.0000 98
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0331452000
_diffrn_orient_matrix_UB_12      0.0001712000
_diffrn_orient_matrix_UB_13      -0.0620955000
_diffrn_orient_matrix_UB_21      0.0671051000
_diffrn_orient_matrix_UB_22      -0.0395883000
_diffrn_orient_matrix_UB_23      0.0623115000
_diffrn_orient_matrix_UB_31      -0.0190781000
_diffrn_orient_matrix_UB_32      -0.1387985000
_diffrn_orient_matrix_UB_33      -0.0178282000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0190
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            7439
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.076
_diffrn_reflns_theta_max         67.076
_diffrn_reflns_theta_min         4.433
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.552
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70615
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.225
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.135
_refine_diff_density_rms         0.028
_refine_ls_extinction_coef       0.00128(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3495
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0588P)^2^+0.5210P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1105
_refine_ls_wR_factor_ref         0.1190
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2794
_reflns_number_total             3495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01733_si_002.cif
_cod_data_source_block           20140222
_cod_database_code               1529884
_chemical_oxdiff_formula         C20H20N1O1F3
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.852
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C23(H23), C24(H24), C25(H25),
  C26(H26)
2.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              94245
_shelx_hkl_checksum              32441
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'