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_1529883
_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         'C19 H17 N O2'
_chemical_formula_sum            'C19 H17 N O2'
_chemical_formula_weight         291.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3862(3)
_cell_length_b                   11.9598(5)
_cell_length_c                   17.2782(7)
_cell_measurement_reflns_used    3742
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.3710
_cell_measurement_theta_min      5.1040
_cell_volume                     1526.31(11)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega    9.00   52.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -180.0000 43

  2 omega  -45.00   23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000  150.0000 68

  3 omega -111.00  -24.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -45.0000 -180.0000 87

  4 omega  -92.00  -63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  125.0000  -30.0000 29

  5 omega   42.00   87.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -180.0000 45

  6 omega   46.00   87.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -60.0000 41

  7 omega   54.00   80.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -30.0000 26

  8 omega   50.00   83.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000    0.0000 33

  9 omega   42.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000 -180.0000 27

 10 omega   62.00   95.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000 -150.0000 33

 11 omega   49.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -90.0000 28

 12 omega   71.00  101.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  178.0000  -60.0000 30

 13 omega  -77.00  -32.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -120.0000 45

 14 omega  -17.00   26.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000    0.0000  120.0000 43

 15 omega  -34.00   17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000  -90.0000 51

 16 omega   -1.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.7033  -57.0000 -180.0000 26

 17 omega   38.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.7033  -57.0000 -180.0000 26

 18 omega   42.00   82.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.4066  -25.0000   60.0000 40

 19 omega   44.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.4066 -111.0000 -180.0000 47

 20 omega   47.00   73.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.4066  -25.0000   30.0000 26

 21 omega  113.00  145.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.4066  -91.0000    0.0000 32

 22 omega   44.00   85.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.4066  -91.0000    0.0000 41

 23 omega   52.00   78.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  150.0000 26

 24 omega   88.00  114.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  150.0000 26

 25 omega   45.00   87.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000 -180.0000 42

 26 omega   58.00   84.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000 -150.0000 26

 27 omega   85.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000 -150.0000 26

 28 omega  150.00  176.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000   30.0000 26

 29 omega   44.00   70.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000  -90.0000 26

 30 omega   79.00  104.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -50.0000  -90.0000 25

 31 omega   53.00   85.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000 -180.0000 32

 32 omega  102.00  129.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000  -60.0000 27

 33 omega  146.00  172.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000  -60.0000 26

 34 omega   64.00   93.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  -90.0000 29

 35 omega   52.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  120.0000 25

 36 omega  110.00  164.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   50.0000 -150.0000 54

 37 omega   64.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000 -150.0000 26

 38 omega   99.00  124.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000 -150.0000 25

 39 omega   91.00  117.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 26

 40 omega  131.00  158.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 27

 41 omega   91.00  117.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000  -60.0000 26

 42 omega  117.00  148.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -12.0000 -180.0000 31
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0247089000
_diffrn_orient_matrix_UB_12      -0.1267752000
_diffrn_orient_matrix_UB_13      0.0118869000
_diffrn_orient_matrix_UB_21      0.0194153000
_diffrn_orient_matrix_UB_22      0.0185906000
_diffrn_orient_matrix_UB_23      0.0878330000
_diffrn_orient_matrix_UB_31      -0.2061587000
_diffrn_orient_matrix_UB_32      -0.0134367000
_diffrn_orient_matrix_UB_33      0.0096843000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9747
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.378
_diffrn_reflns_theta_min         4.496
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97117
_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    1.268
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.145
_refine_diff_density_min         -0.134
_refine_diff_density_rms         0.026
_refine_ls_abs_structure_details
;
 Flack x determined using 1121 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(14)
_refine_ls_extinction_coef       0.0066(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   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3017
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0554P)^2^+0.0895P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0973
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                2834
_reflns_number_total             3017
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01733_si_004.cif
_cod_data_source_block           20140348
_cod_original_cell_volume        1526.31(10)
_cod_database_code               1529883
_chemical_oxdiff_formula         C20H20N2O4
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.880
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C11(H11), C14(H14), C15(H15),
 C17(H17), C18(H18)
2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              55417
_shelx_hkl_checksum              99553
_shelx_shelxl_version_number     2014/7
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'ShelXS (Sheldrick, 2008)'
_olex2_submission_special_instructions 'No special instructions were received'