Unexpected dearomatization of <i>N</i>-protected 5-aminopyrazoles at ambient temperature: a simple route to highly functionalized pyrazolines.
Natarajan, Pradeep; Chatterjee, Arpita; J, Siddharth Jaya Sajeevan; Peruncheralathan, Saravanan; Organic & biomolecular chemistry 22 (2024) 6288–6293; doi:10.1039/d4ob00879k

data_7160055
_publ_section_title
;
 Unexpected dearomatization of <i>N</i>-protected 5-aminopyrazoles at
 ambient temperature: a simple route to highly functionalized pyrazolines.
;
_journal_issue                   31
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6288
_journal_page_last               6293
_journal_paper_doi               10.1039/d4ob00879k
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C25 H23 N3 O4 S'
_chemical_formula_sum            'C25 H23 N3 O4 S'
_chemical_formula_weight         461.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-05-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-24 deposited with the CCDC.	2024-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.061(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6412(4)
_cell_length_b                   10.7301(2)
_cell_length_c                   16.2702(4)
_cell_measurement_reflns_used    14432
_cell_measurement_temperature    259(8)
_cell_measurement_theta_max      78.0700
_cell_measurement_theta_min      3.8580
_cell_volume                     2337.25(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      259(8)
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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   -101.00 -26.00   0.50    0.47    --  -38.50 -60.00 -14.00  150
  2  \w    -51.00  24.00   0.50    0.47    --  -38.50  60.00 125.00  150
  3  \w     37.00 112.00   0.50    0.47    --   49.56  60.00 125.00  150
  4  \w    -13.00  62.00   0.50    0.47    --   49.56 -60.00 -14.00  150
  5  \w     95.00 170.00   0.50    1.91    --  107.46  60.00 125.00  150
  6  \w     45.00 120.00   0.50    1.91    --  107.46 -60.00 -14.00  150
  7  \w    -42.00  28.00   0.50    0.47    --  -38.50  37.00 -90.00  140
  8  \w     28.00  99.00   0.50    0.47    --   49.56-125.00 -30.00  142
  9  \w     28.00  99.00   0.50    0.47    --   49.56-125.00-150.00  142
 10  \w     45.00 121.00   0.50    1.91    --  107.46 -61.00-180.00  152
 11  \w     43.00 108.00   0.50    1.91    --  107.46 -45.00  60.00  130
 12  \w    110.00 167.00   0.50    1.91    --  107.46  77.00 -30.00  114
 13  \w     53.00  95.00   0.50    1.91    --  107.46 -94.00 120.00   84
 14  \w     45.00 111.00   0.50    1.91    --  107.46 -30.00 -90.00  132
 15  \w     46.00 110.00   0.50    1.91    --  107.46 -61.00-120.00  128
 16  \w     40.00 106.00   0.50    1.91    --  107.46 -94.00   0.00  132
 17  \w    100.00 165.00   0.50    1.91    --  107.46 125.00  60.00  130
 18  \w    103.00 169.00   0.50    1.91    --  107.46  77.00 -90.00  132
 19  \w     45.00  70.00   0.50    1.91    --  107.46 -94.00-180.00   50
 20  \w    104.00 166.00   0.50    1.91    --  107.46  77.00  30.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19303
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.274
_diffrn_reflns_theta_min         3.881
_exptl_absorpt_coefficient_mu    1.535
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58727
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
_exptl_crystal_recrystallization_method 'Slow diffussion method'
_exptl_crystal_size_max          0.9
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.281
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.0015(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4885
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0729P)^2^+0.3543P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1217
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4496
_reflns_number_total             4885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00879k2.cif
_cod_data_source_block           5a
_cod_depositor_comments
'Adding full bibliography for 7160054--7160057.cif.'
_cod_database_code               7160055
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.339
_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:
 C6(H6), C5(H5), C24(H24), C2(H2), C3(H3), C28(H28), C17(H17), C15(H15),
 C16(H16), C13(H13), C27(H27), C25(H25), C26(H26), C14(H14)
2.b Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C11(H11A,H11B,H11C)
;
_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
;