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_1529882
_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         'C27 H19 F3 N2'
_chemical_formula_sum            'C27 H19 F3 N2'
_chemical_formula_weight         428.44
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.865(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.4962(3)
_cell_length_b                   17.6328(8)
_cell_length_c                   16.4671(7)
_cell_measurement_reflns_used    2783
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      71.9250
_cell_measurement_theta_min      3.6730
_cell_volume                     2171.65(16)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
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  -65.00  -38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -120.0000 27

  2 omega  -43.00  -17.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   90.0000 26

  3 omega -113.00  -88.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   90.0000 25

  4 omega   -2.00   28.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000 -120.0000 30

  5 omega  -28.00   14.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000   60.0000 42

  6 omega -112.00  -55.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000    0.0000 57

  7 omega -118.00  -38.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000   60.0000 80

  8 omega   21.00   98.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       56.0000 -125.0000    0.0000 77

  9 omega   48.00   90.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000   30.0000 42

 10 omega   52.00  107.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  -30.0000 55

 11 omega   39.00   88.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  150.0000 49

 12 omega   42.00   94.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   30.0000 52

 13 omega   44.00   85.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -150.0000 41

 14 omega  112.00  171.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   90.0000 59

 15 omega   42.00   96.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -60.0000 54

 16 omega   77.00  128.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000  -30.0000 51

 17 omega   89.00  176.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000   60.0000 87

 18 omega  -72.00   26.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -37.0000   60.0000 98
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0096895000
_diffrn_orient_matrix_UB_12      -0.0643337000
_diffrn_orient_matrix_UB_13      0.0627738000
_diffrn_orient_matrix_UB_21      0.0861633000
_diffrn_orient_matrix_UB_22      -0.0548696000
_diffrn_orient_matrix_UB_23      -0.0587842000
_diffrn_orient_matrix_UB_31      0.1869084000
_diffrn_orient_matrix_UB_32      0.0219352000
_diffrn_orient_matrix_UB_33      0.0373405000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0158
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7829
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.677
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.788
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90764
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
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.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.183
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.029
_refine_ls_extinction_coef       0.0032(4)
_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   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         3862
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0742P)^2^+0.3627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1453
_refine_ls_wR_factor_ref         0.1602
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2912
_reflns_number_total             3862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01733_si_003.cif
_cod_data_source_block           20140223
_cod_original_cell_volume        2171.67(16)
_cod_database_code               1529882
_chemical_oxdiff_formula         C20H20N1
_shelx_estimated_absorpt_t_max   0.809
_shelx_estimated_absorpt_t_min   0.770
_reflns_odcompleteness_completeness 99.88
_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. Restrained distances
 C18-F2
 1.35 with sigma of 0.02
 C18-F3A
 1.35 with sigma of 0.02
 C18-F1
 1.35 with sigma of 0.02
 C18-F2A
 1.35 with sigma of 0.02
 C18-F3
 1.35 with sigma of 0.02
 C18-F1A
 1.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2) = Uanis(F2A)
Uanis(F1) = Uanis(F1A)
Uanis(F3) = Uanis(F3A)
4. Others
 Sof(F2A)=Sof(F1A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C20(H20), C21(H21), C24(H24), C25(H25), C26(H26), C27(H27)
5.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              44457
_shelx_hkl_checksum              42501
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'