Synthesis of 2-Aminopyridines via a Base-Promoted Cascade Reaction of N-Propargylic β-Enaminones with Formamides.
Weng, Yunxiang; Kuai, Changsheng; Lv, Weiwei; Cheng, Guolin; The Journal of organic chemistry 83 (2018) 5002–5008; doi:10.1021/acs.joc.8b00128

data_4035515
_publ_section_title
;
 Synthesis of 2-Aminopyridines via a Base-Promoted Cascade Reaction of
 N-Propargylic \b-Enaminones with Formamides.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5002
_journal_page_last               5008
_journal_paper_doi               10.1021/acs.joc.8b00128
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C24 H20 N2'
_chemical_formula_sum            'C24 H20 N2'
_chemical_formula_weight         336.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
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_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_length_a                   10.53852(15)
_cell_length_b                   11.82433(16)
_cell_length_c                   14.4092(2)
_cell_measurement_reflns_used    3619
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.1140
_cell_measurement_theta_min      6.1280
_cell_volume                     1795.54(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_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
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  1 omega    5.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000    0.0000  -90.0000 65

  2 omega  -52.00  -26.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000    0.0000  -90.0000 26

  3 omega   47.00   85.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -77.0000 -120.0000 38

  4 omega   43.00  124.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000 -150.0000 81

  5 omega   -3.00   96.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -99.0000   60.0000 99

  6 omega   35.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   37.0000   30.0000 39

  7 omega   56.00   89.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -180.0000 33

  8 omega   44.00  141.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000 -180.0000 97

  9 omega   41.00   67.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000   30.0000 26

 10 omega   40.00   70.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -120.0000 30

 11 omega  101.00  176.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -30.0000 75

 12 omega   89.00  173.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000   30.0000 84

 13 omega  119.00  173.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -90.0000 54

 14 omega   41.00   78.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  150.0000 37

 15 omega   89.00  115.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000   30.0000 26

 16 omega   -4.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   90.0000 46

 17 omega   35.00   83.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000   90.0000 48
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0684163000
_diffrn_orient_matrix_UB_12      0.0520010000
_diffrn_orient_matrix_UB_13      0.0843514000
_diffrn_orient_matrix_UB_21      -0.0263711000
_diffrn_orient_matrix_UB_22      0.1193696000
_diffrn_orient_matrix_UB_23      -0.0381619000
_diffrn_orient_matrix_UB_31      -0.1264484000
_diffrn_orient_matrix_UB_32      0.0033248000
_diffrn_orient_matrix_UB_33      0.0535613000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0160
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            6131
_diffrn_reflns_point_group_measured_fraction_full 0.917
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        67.063
_diffrn_reflns_theta_max         67.063
_diffrn_reflns_theta_min         4.838
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.561
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.99347
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour
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_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description
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_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.106
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1134 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         2941
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0501P)^2^+0.0627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0857
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_reflns_Friedel_fraction_full    0.826
_reflns_Friedel_fraction_max     0.826
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_reflns_number_total             2941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00128_si_002.cif
_cod_data_source_block           20150461a
_cod_database_code               4035515
_chemical_oxdiff_formula         C20H20N2
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.896
_reflns_odcompleteness_completeness 99.95
_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), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
2.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              85089
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'