Aryne-involved α-C(sp<sup>3</sup>)-H arylation of 4-aminopyrazolones <i>via</i> two distinct systems: dual phase-transfer catalysis and ultraviolet photochemistry.
Chen, Lin; Xu, Shuang; Chen, Zhiming; Organic & biomolecular chemistry 24 (2026) 2261–2269; doi:10.1039/d5ob01838b

data_7160982
_publ_section_title
;
 Aryne-involved &#x3b1;-C(sp<sup>3</sup>)-H arylation of
 4-aminopyrazolones <i>via</i> two distinct systems: dual phase-transfer
 catalysis and ultraviolet photochemistry.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2261
_journal_page_last               2269
_journal_paper_doi               10.1039/d5ob01838b
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C24 H21 N3 O3'
_chemical_formula_sum            'C24 H21 N3 O3'
_chemical_formula_weight         399.44
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-06-22
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-02-06 deposited with the CCDC.	2026-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.723(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2783(3)
_cell_length_b                   13.2651(4)
_cell_length_c                   17.3247(5)
_cell_measurement_reflns_used    10150
_cell_measurement_temperature    127(30)
_cell_measurement_theta_max      72.6720
_cell_measurement_theta_min      3.3340
_cell_volume                     2087.81(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      127(30)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_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     73.00 107.00   0.50    0.10    --   99.00-101.00-120.00   68
  2  \w     34.00  69.00   0.50    0.10    --   99.00-125.00-150.00   70
  3  \w    -12.00  30.00   0.50    0.05    --   45.87-101.00-120.00   84
  4  \w     34.00  64.00   0.50    0.10    --   99.00-125.00  90.00   60
  5  \w     71.00 111.00   0.50    0.10    --   99.00-125.00  90.00   80
  6  \w     35.00  70.00   0.50    0.10    --   99.00 -61.00  60.00   70
  7  \w     27.00  53.00   0.50    0.10    --   99.00 -45.00 150.00   52
  8  \w     28.00  53.00   0.50    0.10    --   99.00 -45.00   0.00   50
  9  \w     28.00  53.00   0.50    0.10    --   99.00 -45.00  30.00   50
 10  \w     27.00  52.00   0.50    0.10    --   99.00 -45.00 -90.00   50
 11  \w     27.00  53.00   0.50    0.10    --   99.00 -45.00-120.00   52
 12  \w     27.00  53.00   0.50    0.10    --   99.00 -45.00-150.00   52
 13  \w    -29.00  28.00   0.50    0.05    --   45.87 -19.00-120.00  114
 14  \w    -16.00  44.00   0.50    0.05    --   45.87 -37.00 120.00  120
 15  \w    124.00 170.00   0.50    0.10    --   99.00 101.00 -16.00   92
 16  \w    -67.00 -27.00   0.50    0.10    --  -99.00  61.00 150.00   80
 17  \w    -59.00 -34.00   0.50    0.10    --  -99.00  61.00  90.00   50
 18  \w    -54.00 -26.00   0.50    0.10    --  -99.00  61.00   0.00   56
 19  \w    -67.00 -39.00   0.50    0.10    --  -99.00  61.00 -30.00   56
 20  \w    -70.00  17.00   0.50    0.05    --  -45.87 101.00 -16.00  174
 21  \w   -102.00 -45.00   0.50    0.10    --  -99.00 101.00 -16.00  114
 22  \w    -87.00 -33.00   0.50    0.10    --  -99.00 125.00-120.00  108
 23  \w    -71.00 -44.00   0.50    0.10    --  -99.00 125.00-150.00   54
 24  \w   -102.00 -74.00   0.50    0.10    --  -99.00 125.00-150.00   56
 25  \w   -173.00-105.00   0.50    0.10    --  -99.00 -30.00  90.00  136
 26  \w   -149.00-100.00   0.50    0.10    --  -99.00-101.00-120.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1008643000
_diffrn_orient_matrix_UB_12      0.0425575000
_diffrn_orient_matrix_UB_13      0.0526515000
_diffrn_orient_matrix_UB_21      -0.0767655000
_diffrn_orient_matrix_UB_22      -0.1032264000
_diffrn_orient_matrix_UB_23      -0.0012853000
_diffrn_orient_matrix_UB_31      0.1126466000
_diffrn_orient_matrix_UB_32      -0.0320512000
_diffrn_orient_matrix_UB_33      0.0739450000
_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  0.0471
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14210
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.010
_diffrn_reflns_theta_min         4.231
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.690
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54758
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.388
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.061
_refine_ls_extinction_coef       0.0052(6)
_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   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4048
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0458
_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^)+(0.1025P)^2^+0.6074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1498
_refine_ls_wR_factor_ref         0.1599
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3621
_reflns_number_total             4048
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01838b2.cif
_cod_data_source_block           chenl-0620
_cod_depositor_comments          'Adding full bibliography for 7160982.cif.'
_cod_database_code               7160982
_shelx_shelxl_version_number     2018/3
_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
2.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              31244
_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 2.005
_oxdiff_exptl_absorpt_empirical_full_min 0.488