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_7160057
_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         'C48 H44 N6 O4 S2'
_chemical_formula_sum            'C48 H44 N6 O4 S2'
_chemical_formula_weight         833.054
_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             2024-05-24
_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                96.635(1)
_cell_angle_beta                 100.372(1)
_cell_angle_gamma                91.122(1)
_cell_formula_units_Z            2
_cell_length_a                   9.4999(1)
_cell_length_b                   13.2071(3)
_cell_length_c                   17.4714(3)
_cell_measurement_reflns_used    26564
_cell_measurement_temperature    297.9(2)
_cell_measurement_theta_max      77.9330
_cell_measurement_theta_min      3.9720
_cell_volume                     2139.98(7)
_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  '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      297.9(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9991
_diffrn_measured_fraction_theta_max 0.9729
_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    -67.00  29.00   0.50    0.41    --  -38.50  86.00 -72.00  192
  2  \w    -10.00  78.00   0.50    0.41    --   49.56 -86.00 169.00  176
  3  \w    102.00 175.00   0.50    1.59    --  107.46  86.00 -72.00  146
  4  \w     40.00 136.00   0.50    1.59    --  107.46 -86.00 169.00  192
  5  \w   -101.00 -27.00   0.50    0.41    --  -38.50 -57.00 150.00  148
  6  \w    -42.00  28.00   0.50    0.41    --  -38.50  37.00  90.00  140
  7  \w    -42.00  28.00   0.50    0.41    --  -38.50  37.00 -90.00  140
  8  \w     31.00 113.00   0.50    0.41    --   49.56  71.00   8.38  164
  9  \w     37.00 112.00   0.50    0.41    --   49.56  61.00 -73.39  150
 10  \w     28.00  99.00   0.50    0.41    --   49.56-125.00-180.00  142
 11  \w     45.00 121.00   0.50    1.59    --  107.46 -61.00 150.00  152
 12  \w     39.00 116.00   0.50    1.59    --  107.46 -15.00-120.00  154
 13  \w     43.00 131.00   0.50    1.59    --  107.46 -77.00 -30.00  176
 14  \w     97.00 170.00   0.50    1.59    --  107.46 125.00-180.00  146
 15  \w     99.00 176.00   0.50    1.59    --  107.46  15.00 -90.00  154
 16  \w     39.00 107.00   0.50    1.59    --  107.46 -94.00  60.00  136
 17  \w     39.00 107.00   0.50    1.59    --  107.46 -94.00 -30.00  136
 18  \w    104.00 174.00   0.50    1.59    --  107.46  38.00-178.39  140
 19  \w     43.00 112.00   0.50    1.59    --  107.46 -45.00 -60.00  138
 20  \w     43.00 112.00   0.50    1.59    --  107.46 -45.00-120.00  138
 21  \w     43.00 112.00   0.50    1.59    --  107.46 -45.00-180.00  138
 22  \w     39.00 111.00   0.50    1.59    --  107.46 -30.00  30.00  144
 23  \w     39.00 107.00   0.50    1.59    --  107.46 -94.00 150.00  136
 24  \w     45.00 113.00   0.50    1.59    --  107.46-125.00 -30.00  136
 25  \w     43.00 112.00   0.50    1.59    --  107.46 -45.00  30.00  138
 26  \w    103.00 172.00   0.50    1.59    --  107.46  77.00 -30.00  138
 27  \w    103.00 172.00   0.50    1.59    --  107.46  77.00  60.00  138
 28  \w     39.00 107.00   0.50    1.59    --  107.46 -94.00-180.00  136
 29  \w     39.00 107.00   0.50    1.59    --  107.46 -94.00  90.00  136
 30  \w     45.00 113.00   0.50    1.59    --  107.46-125.00 -60.00  136
 31  \w    104.00 174.00   0.50    1.59    --  107.46  37.00-149.62  140
 32  \w     38.00  99.00   0.50    0.41    --   49.56  57.00-150.00  122
 33  \w     38.00 113.00   0.50    0.41    --   49.56  57.00  90.00  150
;
_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      -0.0231184000
_diffrn_orient_matrix_UB_12      0.0972852000
_diffrn_orient_matrix_UB_13      0.0532601000
_diffrn_orient_matrix_UB_21      -0.0411197000
_diffrn_orient_matrix_UB_22      -0.0659171000
_diffrn_orient_matrix_UB_23      0.0604425000
_diffrn_orient_matrix_UB_31      0.1581139000
_diffrn_orient_matrix_UB_32      0.0021511000
_diffrn_orient_matrix_UB_33      0.0408054000
_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  0.0302
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.9991
_diffrn_reflns_Laue_measured_fraction_max 0.9729
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34700
_diffrn_reflns_point_group_measured_fraction_full 0.9991
_diffrn_reflns_point_group_measured_fraction_max 0.9729
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         78.84
_diffrn_reflns_theta_min         4.00
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.546
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84722
_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    1.293
_exptl_crystal_description       needle
_exptl_crystal_F_000             880.032
_exptl_crystal_recrystallization_method 'Slow diffusion method'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.3081
_refine_diff_density_min         -0.3190
_refine_diff_density_rms         0.0365
_refine_ls_d_res_high            0.7858
_refine_ls_d_res_low             11.0608
_refine_ls_extinction_coef       0.0087(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0372
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    114
_refine_ls_number_parameters     693
_refine_ls_number_reflns         8982
_refine_ls_number_restraints     479
_refine_ls_restrained_S_all      1.0085
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0417
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0633P)^2^+0.4761P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1169
_refine_ls_wR_factor_ref         0.1187
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -12
_reflns_limit_k_max              16
_reflns_limit_k_min              -16
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                8295
_reflns_number_total             8982
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4ob00879k2.cif
_cod_data_source_block           14h
_cod_depositor_comments
'Adding full bibliography for 7160054--7160057.cif.'
_cod_database_code               7160057
_chemical_oxdiff_formula         'C H N O S'
_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) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C45A-C43 \\sim C45B-C43 \\sim C46A-C45A \\sim C46B-C45B \\sim C47-C46A \\sim
C47-C46B \\sim C48B-C47
 \\sim C48A-C47 \\sim C48B-C44B \\sim C48A-C44A \\sim C44B-C43 \\sim C44A-C43
 with sigma of 0.01
 C43-C47 \\sim C44B-C48B \\sim C45B-C46B \\sim C44A-C48A \\sim C46A-C45A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C45B \\sim C46B \\sim C46A \\sim C45A \\sim C44B \\sim C48B \\sim C48A \\sim
C44A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
C23B \\sim C24B \\sim C28B \\sim C26B \\sim C25B \\sim C27B \\sim C23A \\sim
C24A \\sim C26A \\sim C27A \\sim C28A \\sim C25A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C30B \\sim C31B \\sim C32B \\sim C35B \\sim C34B \\sim C33B \\sim C30A \\sim
C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
4. Others
 Sof(H47a)=Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46B)=Sof(C44A)=Sof(H44A)=
 Sof(C48A)=Sof(H48A)=1-FVAR(1)
 Sof(H47)=Sof(C44B)=Sof(H44B)=Sof(C48B)=Sof(H48B)=Sof(C46A)=Sof(H46A)=
 Sof(C45A)=Sof(H45A)=FVAR(1)
 Sof(H22c)=Sof(H22d)=Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C28B)=Sof(H28B)=
 Sof(C26B)=Sof(H26B)=Sof(C25B)=Sof(H25B)=Sof(C27B)=Sof(H27B)=1-FVAR(2)
 Sof(H22a)=Sof(H22b)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=FVAR(2)
 Sof(C30B)=Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=Sof(C35B)=Sof(H35B)=
 Sof(C34B)=Sof(H34B)=Sof(C33B)=Sof(H33B)=1-FVAR(3)
 Sof(C30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=
 Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C22(H22c,H22d), C22(H22a,H22b), C4(H4a,H4b)
5.b Aromatic/amide H refined with riding coordinates:
 C37(H37), C6(H6), C10(H10), C41(H41), C40(H40), C38(H38), C13(H13),
 C24B(H24B), C47(H47), C47(H47a), C9(H9), C31B(H31B), C7(H7), C17(H17),
 C14(H14), C8(H8), C28B(H28B), C16(H16), C26B(H26B), C44B(H44B), C32B(H32B),
 C25B(H25B), C35B(H35B), C27B(H27B), C48B(H48B), C45B(H45B), C46B(H46B),
 C34B(H34B), C33B(H33B), C44A(H44A), C48A(H48A), C46A(H46A), C45A(H45A),
 C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A), C31A(H31A),
 C32A(H32A), C33A(H33A), C34A(H34A), C35A(H35A)
5.c Idealised Me refined as rotating group:
 C11(H11a,H11b,H11c), C29(H29a,H29b,H29c), C42(H42a,H42b,H42c), C18(H18a,H18b,
 H18c)
;
_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 1.206
_oxdiff_exptl_absorpt_empirical_full_min 0.801