An isoxazole strategy for the synthesis of alkyl 5-amino-4-cyano-1<i>H</i>-pyrrole-2-carboxylates - versatile building blocks for assembling pyrrolo-fused heterocycles.
Agafonova, Anastasiya V.; Funt, Liya D.; Novikov, Mikhail S.; Khlebnikov, Alexander F.; Organic & biomolecular chemistry 19 (2021) 1976–1984; doi:10.1039/d1ob00053e

data_7157866
_publ_section_title
;
 An isoxazole strategy for the synthesis of alkyl
 5-amino-4-cyano-1<i>H</i>-pyrrole-2-carboxylates - versatile building
 blocks for assembling pyrrolo-fused heterocycles.
;
_journal_issue                   9
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1976
_journal_page_last               1984
_journal_paper_doi               10.1039/d1ob00053e
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C13 H11 N3 O2'
_chemical_formula_sum            'C13 H11 N3 O2'
_chemical_formula_weight         241.25
_chemical_name_systematic
'methyl 5-amino-4-cyano-3-phenyl-1H-pyrrole-2-carboxylate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc26yb8s
_audit_creation_date             2020-12-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-05 deposited with the CCDC.	2021-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                85.469(3)
_cell_angle_beta                 82.621(3)
_cell_angle_gamma                73.765(3)
_cell_formula_units_Z            4
_cell_length_a                   7.2529(3)
_cell_length_b                   12.9297(5)
_cell_length_c                   13.0243(5)
_cell_measurement_reflns_used    9216
_cell_measurement_temperature    99.99(13)
_cell_measurement_theta_max      75.9070
_cell_measurement_theta_min      3.5340
_cell_volume                     1161.78(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     17.00 105.00   1.00    3.50    --   40.38  38.00  60.00   88
  2  \w     82.00 176.00   1.00    8.00    --  113.00  30.00   0.00   94
  3  \w    125.00 176.00   1.00    8.00    --  113.00  77.00 -60.00   51
  4  \w    151.00 177.00   1.00    8.00    --  113.00  15.00-120.00   26
  5  \w    119.00 176.00   1.00    8.00    --  113.00 112.00-120.00   57
  6  \w    107.00 177.00   1.00    8.00    --  113.00  61.00 -90.00   70
  7  \w     97.00 128.00   1.00    3.50    --   40.38 178.00-120.00   31
  8  \w     83.00 110.00   1.00    3.50    --   40.38 178.00-180.00   27
  9  \w     85.00 165.00   1.00    8.00    --  113.00  61.00  30.00   80
 10  \w    103.00 139.00   1.00    8.00    --  113.00 -61.00 -60.00   36
 11  \w     83.00 109.00   1.00    8.00    --  113.00 -95.00-120.00   26
 12  \w     49.00 110.00   1.00    8.00    --  113.00-112.00-180.00   61
 13  \w     39.00 131.00   1.00    8.00    --  113.00 -45.00-180.00   92
 14  \w     75.00 115.00   1.00    8.00    --  113.00-112.00   0.00   40
 15  \w     82.00 108.00   1.00    8.00    --  113.00 -95.00   0.00   26
 16  \w     42.00 100.00   1.00    8.00    --  113.00 -61.00 -60.00   58
 17  \w     32.00 106.00   1.00    8.00    --  113.00 -95.00-150.00   74
 18  \w     35.00 113.00   1.00    8.00    --  113.00-112.00 120.00   78
 19  \w   -103.00 -15.00   1.00    3.50    --  -40.38 -38.00-180.00   88
 20  \w   -126.00 -48.00   1.00    3.50    --  -40.38-178.00-150.00   78
 21  \w   -109.00 -14.00   1.00    3.50    --  -40.38 -38.00  90.00   95
 22  \w     83.00 110.00   1.00    8.00    --  113.00  65.00  -2.00   27
 23  \w    -67.00  -5.00   1.00    3.50    --  -40.38  38.00 -60.00   62
 24  \w    -91.00 -41.00   1.00    3.50    --  -40.38 -57.00 -30.00   50
 25  \w    -69.00  31.00   1.00    3.50    --  -40.38  57.00 150.00  100
 26  \w    -39.00 -11.00   1.00    3.50    --  -40.38 -57.00 -30.00   28
 27  \w      7.00  32.00   1.00    3.50    --   44.00  88.00-118.93   25
 28  \w     12.00  37.00   1.00    3.50    --   48.00  84.00  93.74   25
 29  \w     12.00  37.00   1.00    3.50    --   48.00  84.00  37.94   25
 30  \w     22.00  48.00   1.00    3.50    --   56.00  77.00 163.53   26
 31  \w     25.00  54.00   1.00    3.50    --   56.00  76.00 -28.69   29
 32  \w     28.00  54.00   1.00    3.50    --   60.00  76.00 122.98   26
 33  \w     31.00  59.00   1.00    3.50    --   64.00  76.00 -78.47   28
 34  \w     35.00  61.00   1.00    3.50    --   68.00  77.00  67.47   26
 35  \w     35.00  60.00   1.00    3.50    --   68.00  75.00  12.15   25
 36  \w     38.00  74.00   1.00    3.50    --   68.00  74.00-138.51   36
 37  \w    102.00 128.00   1.00    3.50    --   72.00  76.00 160.63   26
 38  \w     39.00  65.00   1.00    3.50    --   72.00  76.00 160.63   26
 39  \w    101.00 127.00   1.00    3.50    --   76.00  70.00-174.26   26
 40  \w     44.00  70.00   1.00    3.50    --   76.00  70.00-174.26   26
 41  \w     52.00  78.00   1.00    8.00    --   84.00  69.00 -44.85   26
 42  \w    126.00 152.00   1.00    8.00    --   84.00  75.00   4.10   26
 43  \w     52.00  78.00   1.00    8.00    --   84.00  75.00   4.10   26
 44  \w     56.00  82.00   1.00    8.00    --   88.00  72.00 109.67   26
 45  \w    133.00 161.00   1.00    8.00    --   88.00  61.00 -53.27   28
 46  \w     58.00  88.00   1.00    8.00    --   88.00  61.00 -53.27   30
 47  \w     90.00 154.00   1.00    8.00    --   88.00  70.00 178.00   64
 48  \w     56.00  83.00   1.00    8.00    --   88.00  70.00 178.00   27
 49  \w     61.00  87.00   1.00    8.00    --   92.00  64.00  66.87   26
 50  \w     64.00  92.00   1.00    8.00    --   92.00  58.00 -83.94   28
 51  \w     59.00  85.00   1.00    8.00    --   92.00  73.00 -21.79   26
 52  \w     61.00  87.00   1.00    8.00    --   92.00  64.00 144.75   26
 53  \w     64.00  94.00   1.00    8.00    --   96.00  73.00  68.72   30
 54  \w     79.00 106.00   1.00    8.00    --  113.00  77.00  30.00   27
 55  \w     79.00 105.00   1.00    8.00    --  113.00  77.00   0.00   26
 56  \w     79.00 111.00   1.00    8.00    --  113.00  77.00-180.00   32
 57  \w     79.00 104.00   1.00    8.00    --  113.00  77.00 -30.00   25
 58  \w     86.00 113.00   1.00    8.00    --  113.00  61.00-150.00   27
 59  \w     79.00 168.00   1.00    8.00    --  113.00  77.00  90.00   89
 60  \w     86.00 112.00   1.00    8.00    --  113.00  45.00 -90.00   26
 61  \w    112.00 137.00   1.00    8.00    --  113.00  77.00-150.00   25
 62  \w     84.00 111.00   1.00    8.00    --  113.00  61.00 -90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1167395000
_diffrn_orient_matrix_UB_12      0.1146150000
_diffrn_orient_matrix_UB_13      0.0302611000
_diffrn_orient_matrix_UB_21      0.1263028000
_diffrn_orient_matrix_UB_22      0.0478876000
_diffrn_orient_matrix_UB_23      -0.0840491000
_diffrn_orient_matrix_UB_31      -0.1413288000
_diffrn_orient_matrix_UB_32      0.0014493000
_diffrn_orient_matrix_UB_33      -0.0792149000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16032
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        62.490
_diffrn_reflns_theta_max         62.490
_diffrn_reflns_theta_min         3.425
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.793
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66001
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       prism
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.238
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         3695
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0341
_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^)+(0.0490P)^2^+0.4865P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0881
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3304
_reflns_number_total             3695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00053e2.cif
_cod_data_source_block           7060-11161_lia501
_cod_depositor_comments          'Adding full bibliography for 7157866.cif.'
_cod_database_code               7157866
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C13 H11 N5 O3'
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.897
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N1'(H1'), C13(H13), C9'(H9'), C9(H9), C10'(H10'), C13'(H13'),
 C12(H12), C10(H10), C12'(H12'), C11(H11), C11'(H11')
2.b X=CH2 refined with riding coordinates:
 N2(H2A,H2B), N2'(H2'A,H2'B)
2.c Idealised Me refined as rotating group:
 C7'(H7'A,H7'B,H7'C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              37367
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.103
_oxdiff_exptl_absorpt_empirical_full_min 0.538