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_7160054
_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         'C23 H21 N3 O3 S'
_chemical_formula_sum            'C23 H21 N3 O3 S'
_chemical_formula_weight         419.508
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_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                86.767(1)
_cell_angle_beta                 79.589(1)
_cell_angle_gamma                76.363(1)
_cell_formula_units_Z            2
_cell_length_a                   8.4579(1)
_cell_length_b                   11.1076(2)
_cell_length_c                   11.4172(2)
_cell_measurement_reflns_used    11060
_cell_measurement_temperature    295.77(3)
_cell_measurement_theta_max      75.1000
_cell_measurement_theta_min      4.0840
_cell_volume                     1025.11(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.77(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9973
_diffrn_measured_fraction_theta_max 0.9702
_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    -96.00 -10.00   0.50    0.50    --  -38.50 137.00  31.00  172
  2  \w    -94.00  -6.00   0.50    0.50    --  -38.50 132.00-146.00  176
  3  \w     31.00 107.00   0.50    0.50    --   49.31-137.00 -32.00  152
  4  \w     39.00 123.00   0.50    2.00    --  102.63-132.00 144.00  168
  5  \w     40.00 127.00   0.50    2.00    --  102.63-137.00 -32.00  174
  6  \w     91.00 166.00   0.50    2.00    --  102.63 132.00-146.00  150
  7  \w     87.00 166.00   0.50    2.00    --  102.63 137.00  31.00  158
  8  \w    -44.00  31.00   0.50    0.50    --  -38.50  19.00 -30.00  150
  9  \w   -101.00 -27.00   0.50    0.50    --  -38.50 -57.00 -30.00  148
 10  \w    -42.00  28.00   0.50    0.50    --  -38.50  37.00-150.00  140
 11  \w     27.00 105.00   0.50    0.50    --   49.31-132.00 144.00  156
 12  \w    -13.00  61.00   0.50    0.50    --   49.31 -57.00 -30.00  148
 13  \w     46.00 116.00   0.50    0.50    --   49.31  37.00 -90.00  140
 14  \w     38.00 107.00   0.50    2.00    --  102.63 -45.00 -30.00  138
 15  \w     95.00 171.00   0.50    2.00    --  102.63  15.00 -60.00  152
 16  \w     99.00 171.00   0.50    2.00    --  102.63  30.00-150.00  144
 17  \w     99.00 171.00   0.50    2.00    --  102.63  30.00-120.00  144
 18  \w     38.00 107.00   0.50    2.00    --  102.63 -45.00 -90.00  138
 19  \w     38.00 107.00   0.50    2.00    --  102.63 -45.00  60.00  138
 20  \w     38.00 126.00   0.50    2.00    --  102.63 -77.00 -30.00  176
 21  \w     34.00 110.00   0.50    2.00    --  102.63 -94.00  60.00  152
 22  \w     40.00 116.00   0.50    2.00    --  102.63 -61.00  90.00  152
 23  \w     38.00 126.00   0.50    2.00    --  102.63 -77.00 150.00  176
 24  \w     34.00 111.00   0.50    2.00    --  102.63 -15.00-180.00  154
 25  \w     95.00 171.00   0.50    2.00    --  102.63  15.00-180.00  152
 26  \w     40.00 116.00   0.50    2.00    --  102.63 -61.00 150.00  152
 27  \w     98.00 167.00   0.50    2.00    --  102.63  45.00-180.00  138
 28  \w     38.00 107.00   0.50    2.00    --  102.63 -45.00-180.00  138
 29  \w     40.00 116.00   0.50    2.00    --  102.63 -61.00 -90.00  152
 30  \w     99.00 171.00   0.50    2.00    --  102.63  30.00 -30.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0348030000
_diffrn_orient_matrix_UB_12      0.0021672000
_diffrn_orient_matrix_UB_13      0.1371456000
_diffrn_orient_matrix_UB_21      -0.0098033000
_diffrn_orient_matrix_UB_22      -0.1369439000
_diffrn_orient_matrix_UB_23      0.0037533000
_diffrn_orient_matrix_UB_31      0.1868149000
_diffrn_orient_matrix_UB_32      -0.0401809000
_diffrn_orient_matrix_UB_33      0.0016338000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 0.9973
_diffrn_reflns_Laue_measured_fraction_max 0.9702
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14687
_diffrn_reflns_point_group_measured_fraction_full 0.9973
_diffrn_reflns_point_group_measured_fraction_max 0.9702
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         75.43
_diffrn_reflns_theta_min         3.94
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.655
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77918
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
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    1.359
_exptl_crystal_description       needle
_exptl_crystal_F_000             442.083
_exptl_crystal_recrystallization_method 'Slow diffusion method'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.2871
_refine_diff_density_min         -0.4675
_refine_diff_density_rms         0.0738
_refine_ls_d_res_high            0.7965
_refine_ls_d_res_low             11.2281
_refine_ls_goodness_of_fit_ref   1.0332
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    49
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4139
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.0237
_refine_ls_R_factor_all          0.0612
_refine_ls_R_factor_gt           0.0557
_refine_ls_shift/su_max          -0.0010
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1184P)^2^+0.2107P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1624
_refine_ls_wR_factor_ref         0.1736
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              13
_reflns_limit_k_min              -13
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                3689
_reflns_number_total             4139
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4ob00879k2.cif
_cod_data_source_block           7a
_cod_depositor_comments
'Adding full bibliography for 7160054--7160057.cif.'
_cod_database_code               7160054
_chemical_oxdiff_formula         'C46 H42 N4 O8 S2 '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
C9A \\sim C8A \\sim C8B \\sim C9B \\sim C5A \\sim C6A \\sim C6B \\sim C5B:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Others
 Sof(H7b)=Sof(C9B)=Sof(H9B)=Sof(C8B)=Sof(H8B)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=1-FVAR(1)
 Sof(H7a)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C9A)=Sof(H9A)=Sof(C8A)=
 Sof(H8A)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C18(H18), C11(H11), C22(H22), C21(H21), C15(H15), C19(H19), C13(H13),
 C12(H12), C14(H14), C7(H7b), C7(H7a), C9B(H9B), C8B(H8B), C5B(H5B), C6B(H6B),
 C9A(H9A), C8A(H8A), C5A(H5A), C6A(H6A)
4.b Idealised Me refined as rotating group:
 C23(H23a,H23b,H23c), C16(H16a,H16b,H16c)
4.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 3.309
_oxdiff_exptl_absorpt_empirical_full_min 0.260