Copper-catalysed decarboxylative alkynylation-cyclization reaction of propargylic cyclic carbonates with nitrile imines to access tetrasubstituted pyrazoles.
Yu, Xiaowen; Li, Jinxia; Duan, Jiongjiong; Fan, Feifei; Xie, Huanping; Huang, Yanfan; Shi, Shukui; Kong, Weiguang; Li, Ting; Chemical communications (Cambridge, England) 62 (2026) 6600–6603; doi:10.1039/d5cc06713h

data_7135569
_publ_section_title
;
 Copper-catalysed decarboxylative alkynylation-cyclization reaction of
 propargylic cyclic carbonates with nitrile imines to access
 tetrasubstituted pyrazoles.
;
_journal_issue                   24
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6600
_journal_page_last               6603
_journal_paper_doi               10.1039/d5cc06713h
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C29 H19 F3 N2 O3'
_chemical_formula_sum            'C29 H19 F3 N2 O3'
_chemical_formula_weight         500.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-26 deposited with the CCDC.	2026-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.663(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.74880(10)
_cell_length_b                   8.7541(2)
_cell_length_c                   36.3995(7)
_cell_measurement_reflns_used    25475
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      78.7950
_cell_measurement_theta_min      2.4150
_cell_volume                     2457.06(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.118a 64-bit (release 27-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_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 0.995
_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    -70.00 -32.00   0.50    0.45    -- -105.00  61.00 150.00   76
  2  \w    -66.00 -34.00   0.50    0.45    -- -105.00  61.00 120.00   64
  3  \w    -61.00  22.00   0.50    0.08    --  -46.39  57.00  90.00  166
  4  \w    -25.00  23.00   0.50    0.08    --  -46.39  19.00  60.00   96
  5  \w    -71.00 -46.00   0.50    0.45    -- -105.00  61.00 -30.00   50
  6  \w    -18.00  27.00   0.50    0.08    --  -46.39  19.00-150.00   90
  7  \w   -107.00 -80.00   0.50    0.45    -- -105.00 109.00 -29.10   54
  8  \w   -111.00 -86.00   0.50    0.45    -- -105.00 125.00 -30.00   50
  9  \w    -77.00 -36.00   0.50    0.45    -- -105.00 153.00 161.69   82
 10  \w   -131.00 -80.00   0.50    0.45    -- -105.00 153.00 161.69  102
 11  \w   -126.00 -41.00   0.50    0.45    -- -105.00 145.00 112.32  170
 12  \w   -112.00 -48.00   0.50    0.45    -- -105.00 125.00  90.00  128
 13  \w   -106.00 -41.00   0.50    0.45    -- -105.00 125.00 120.00  130
 14  \w   -107.00 -45.00   0.50    0.45    -- -105.00 109.00  70.96  124
 15  \w   -111.00 -86.00   0.50    0.45    -- -105.00 125.00   0.00   50
 16  \w    -64.00 -38.00   0.50    0.45    -- -105.00 125.00 -30.00   52
 17  \w    -64.00 -37.00   0.50    0.45    -- -105.00 109.00 -29.10   54
 18  \w   -112.00 -52.00   0.50    0.45    -- -105.00 125.00-120.00  120
 19  \w   -118.00 -31.00   0.50    0.08    --  -46.39 -19.00 -90.00  174
 20  \w   -175.00 -90.00   0.50    0.45    -- -105.00 -45.00 -30.00  170
 21  \w   -168.00 -87.00   0.50    0.45    -- -105.00 -61.00-120.00  162
 22  \w     63.00  98.00   0.50    0.45    --  113.25 -77.00  30.00   70
 23  \w     77.00 105.00   0.50    0.45    --  113.25 -77.00 -30.00   56
 24  \w     42.00  69.00   0.50    0.45    --  113.25 -61.00   0.00   54
 25  \w    -25.00  62.00   0.50    0.08    --   46.39 -57.00 -90.00  174
 26  \w     84.00 119.00   0.50    0.08    --   46.39 178.00-120.00   70
 27  \w     44.00 103.00   0.50    0.45    --  113.25 -77.00-120.00  118
 28  \w     45.00  71.00   0.50    0.45    --  113.25 -61.00 -90.00   52
 29  \w     47.00  79.00   0.50    0.45    --  113.25 -95.00 -30.00   64
 30  \w     49.00 110.00   0.50    0.45    --  113.25-125.00  30.00  122
 31  \w     48.00  77.00   0.50    0.45    --  113.25-125.00-120.00   58
 32  \w     97.00 176.00   0.50    0.45    --  113.25  61.00  60.00  158
 33  \w    133.00 174.00   0.50    0.45    --  113.25  77.00  30.00   82
 34  \w     90.00 131.00   0.50    0.45    --  113.25  77.00  30.00   82
 35  \w    111.00 159.00   0.50    0.45    --  113.25  30.00  30.00   96
 36  \w     96.00 136.00   0.50    0.45    --  113.25  15.00 150.00   80
 37  \w    148.00 174.00   0.50    0.45    --  113.25  15.00 150.00   52
 38  \w     74.00 118.00   0.50    0.08    --   46.39  57.00  60.00   88
 39  \w     30.00  71.00   0.50    0.08    --   46.39  57.00  60.00   82
 40  \w    101.00 127.00   0.50    0.45    --  113.25  15.00-180.00   52
 41  \w    140.00 175.00   0.50    0.45    --  113.25  15.00-180.00   70
 42  \w     22.00  47.00   0.50    0.08    --   47.73-114.00  82.00   50
 43  \w    -78.00 -52.00   0.50    0.45    -- -105.00 144.00 -80.62   52
 44  \w   -126.00-101.00   0.50    0.45    -- -105.00 144.00  19.44   50
 45  \w   -108.00 -82.00   0.50    0.45    -- -105.00 109.00 175.65   52
 46  \w     59.00 102.00   0.50    0.45    --  113.25 -95.00-120.00   86
 47  \w   -120.00 -24.00   0.50    0.08    --  -47.73 -77.00 120.00  192
 48  \w   -120.00 -31.00   0.50    0.08    --  -47.73 -57.00 -90.00  178
 49  \w   -120.00 -31.00   0.50    0.08    --  -47.73 -57.00  30.00  178
 50  \w   -120.00 -24.00   0.50    0.08    --  -47.73 -77.00-150.00  192
 51  \w   -120.00 -31.00   0.50    0.08    --  -47.73 -57.00 120.00  178
 52  \w   -120.00 -24.00   0.50    0.08    --  -47.73 -77.00 -90.00  192
 53  \w    -26.00  28.00   0.50    0.08    --  -47.73  19.00 -30.00  108
 54  \w   -120.00 -24.00   0.50    0.08    --  -47.73 -77.00  30.00  192
 55  \w   -120.00 -24.00   0.50    0.08    --  -47.73 -77.00   0.00  192
 56  \w   -175.00-111.00   0.50    0.45    -- -105.00 -61.00  12.77  128
 57  \w   -175.00 -88.00   0.50    0.45    -- -105.00 -54.00 -74.44  174
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0120617000
_diffrn_orient_matrix_UB_12      -0.1402163000
_diffrn_orient_matrix_UB_13      -0.0128190000
_diffrn_orient_matrix_UB_21      -0.0517260000
_diffrn_orient_matrix_UB_22      -0.1001153000
_diffrn_orient_matrix_UB_23      0.0165228000
_diffrn_orient_matrix_UB_31      -0.1915865000
_diffrn_orient_matrix_UB_32      0.0358398000
_diffrn_orient_matrix_UB_33      -0.0038260000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0599
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            42565
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.591
_diffrn_reflns_theta_max         66.591
_diffrn_reflns_theta_min         2.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.874
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61762
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.783
_refine_diff_density_min         -0.635
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         4321
_refine_ls_number_restraints     355
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1460
_refine_ls_R_factor_gt           0.1414
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0100P)^2^+20.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2746
_refine_ls_wR_factor_ref         0.2760
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3926
_reflns_number_total             4321
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06713h2.cif
_cod_data_source_block           p21m
_cod_depositor_comments
'Adding full bibliography for 7135569--7135570.cif.'
_cod_database_code               7135569
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         chno
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H8A,H8B} of C8
 At 1.5 times of:
  {H17A,H17B} of C17
2. Restrained distances
 C17-H17B = C17-H17A
 0.85 with sigma of 0.01
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5.a Riding coordinates:
 C17(H17A,H17B)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C19(H19), C20(H20), C21(H21),
 C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29)
5.d Fitted hexagon refined as free rotating group:
 C6(C1,C2,C3,C4,C5)
;
_shelx_res_checksum              22176
_shelx_hkl_checksum              48424
_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 1.520
_oxdiff_exptl_absorpt_empirical_full_min 0.661