The Elusive Paal-Knorr Intermediates in the Trofimov Synthesis of Pyrroles: Experimental and Theoretical Studies.
Sączewski, Jarosław; Fedorowicz, Joanna; Gdaniec, Maria; Wiśniewska, Paulina; Sieniawska, Emilia; Drażba, Zuzanna; Rzewnicka, Justyna; Balewski, Łukasz; The Journal of organic chemistry 82 (2017) 9737–9743; doi:10.1021/acs.joc.7b01851

data_4033077
_publ_section_title
;
 The Elusive Paal-Knorr Intermediates in the Trofimov Synthesis of
 Pyrroles: Experimental and Theoretical Studies.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9737
_journal_page_last               9743
_journal_paper_doi               10.1021/acs.joc.7b01851
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H16 N2 O4'
_chemical_formula_sum            'C14 H16 N2 O4'
_chemical_formula_weight         276.29
_chemical_name_systematic
;
(E)-Ethyl 3-(4,6-dimethyl-3-
oxoisoxazolo[3,4-b]pyridin-1(3H)-yl)but-2-enoate (2b)
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-07-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.115(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   4.07910(10)
_cell_length_b                   8.7997(2)
_cell_length_c                   19.3763(4)
_cell_measurement_reflns_used    3910
_cell_measurement_temperature    297.40(14)
_cell_measurement_theta_max      75.2510
_cell_measurement_theta_min      4.5590
_cell_volume                     695.04(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.40(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5357
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_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   -115.00 -11.00   1.00    2.39    --  -40.96 -57.00-150.00  104
  2  \w      2.00  98.00   1.00    2.39    --   40.96-125.00-180.00   96
  3  \w     15.00 117.00   1.00    2.39    --   40.96  37.00 -60.00  102
  4  \w     33.00  69.00   1.00    9.54    --  111.05 -30.00   0.00   36
  5  \w     33.00  69.00   1.00    9.54    --  111.05 -30.00  30.00   36
  6  \w     37.00 141.00   1.00    9.54    --  111.05 -61.00  60.00  104
  7  \w     33.00  69.00   1.00    9.54    --  111.05 -30.00 -30.00   36
  8  \w     33.00 116.00   1.00    9.54    --  111.05-111.00 -60.00   83
  9  \w     50.00 158.00   1.00    9.54    --  111.05  15.00 -90.00  108
 10  \w     27.00 109.00   1.00    9.54    --  111.05 -94.00   0.00   82
 11  \w     27.00 109.00   1.00    9.54    --  111.05 -94.00 -30.00   82
 12  \w    -67.00  35.00   1.00    2.39    --  -40.96  37.00   0.00  102
 13  \w   -120.00  -7.00   1.00    2.39    --  -40.96 -77.00  90.00  113
 14  \w     15.00 117.00   1.00    2.39    --   40.96  37.00  30.00  102
 15  \w     81.00 158.00   1.00    9.54    --  111.05  61.00 -60.00   77
 16  \w     83.00 158.00   1.00    9.54    --  111.05  45.00 120.00   75
 17  \w     36.00  63.00   1.00    9.54    --  111.05 -45.00-180.00   27
 18  \w     50.00 158.00   1.00    9.54    --  111.05  15.00  60.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0128796000
_diffrn_orient_matrix_UB_12      0.1733764000
_diffrn_orient_matrix_UB_13      0.0107716000
_diffrn_orient_matrix_UB_21      -0.0610268000
_diffrn_orient_matrix_UB_22      0.0241672000
_diffrn_orient_matrix_UB_23      -0.0781659000
_diffrn_orient_matrix_UB_31      -0.3727429000
_diffrn_orient_matrix_UB_32      0.0020261000
_diffrn_orient_matrix_UB_33      0.0102222000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            5642
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.625
_diffrn_reflns_theta_min         2.282
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.815
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76197
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            clear
_exptl_crystal_colour_lustre     clear
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       needle
_exptl_crystal_F_000             292
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.092
_refine_diff_density_min         -0.132
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1009 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.12(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     187
_refine_ls_number_reflns         2585
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0315
_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^)+(0.0488P)^2^+0.0138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0819
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.896
_reflns_Friedel_fraction_max     0.823
_reflns_number_gt                2483
_reflns_number_total             2585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           2b
_cod_database_code               4033077
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_usercomment     '293, COLOURLESS'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(2)
 Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(2)
3.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C14(H14)
3.c Disordered Me refined as rotating group:
 C11(H11A,H11B,H11C,H11D,H11E,H11F), C12(H12A,H12B,H12C,H12D,H12E,H12F)
3.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_olex2_submission_original_sample_id jf112
_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 1.487
_oxdiff_exptl_absorpt_empirical_full_min 0.499