Diastereoselective construction of spiro-cyclopropyl-pyrazoles <i>via</i> a [2 + 1] annulation reaction of iminoindoline-derived alkenes and 4-bromo-pyrazolones.
Hu, Dan; Yin, Heng; Li, Fuyu; He, Jiao; Deng, Chenlong; Liu, Lixia; Xia, Wen; Li, Yulong; Li, Chenyi; Organic & biomolecular chemistry 24 (2026) 1063–1068; doi:10.1039/d5ob01841b

data_7160957
_publ_section_title
;
 Diastereoselective construction of spiro-cyclopropyl-pyrazoles <i>via</i>
 a [2 + 1] annulation reaction of iminoindoline-derived alkenes and
 4-bromo-pyrazolones.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1063
_journal_page_last               1068
_journal_paper_doi               10.1039/d5ob01841b
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C32 H26 Br N4 O3 S'
_chemical_formula_sum            'C32 H26 Br N4 O3 S'
_chemical_formula_weight         626.54
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-19 deposited with the CCDC.	2026-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                84.6530(10)
_cell_angle_beta                 78.8130(10)
_cell_angle_gamma                78.2160(10)
_cell_formula_units_Z            4
_cell_length_a                   11.1261(4)
_cell_length_b                   12.1877(4)
_cell_length_c                   24.0151(8)
_cell_measurement_reflns_used    9939
_cell_measurement_temperature    297.00
_cell_measurement_theta_max      22.76
_cell_measurement_theta_min      2.30
_cell_volume                     3122.41(18)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      297.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0806
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            79843
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.300
_diffrn_reflns_theta_min         1.901
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.421
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6446
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1051 before and 0.0654 after correction.
The Ratio of minimum to maximum transmission is 0.8644.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             1284
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.056
_refine_diff_density_min         -1.690
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         15497
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.1189
_refine_ls_R_factor_gt           0.0704
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1396P)^2^+0.8384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2164
_refine_ls_wR_factor_ref         0.2521
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8586
_reflns_number_total             15497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01841b2.cif
_cod_data_source_block           mo_250226lcy_0m
_cod_database_code               7160957
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.764
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C80(H80), C13(H13)
2.b Aromatic/amide H refined with riding coordinates:
 N94(H94), N25(H25), N26(H26), N93(H93), C92(H92), C75(H75), C28(H28),
 C99(H99), C71(H71), C72(H72), C105(H105), C7(H7), C36(H36), C74(H74),
 C101(H101), C38(H38), C108(H108), C45(H45), C39(H39), C8(H8), C51(H51), C4(H4),
  C106(H106), C114(H114), C58(H58), C52(H52), C5(H5), C118(H118), C121(H121),
 C40(H40), C116(H116), C124(H124), C48(H48), C1(H1), C119(H119), C55(H55),
 C126(H126), C50(H50)
2.c Idealised Me refined as rotating group:
 C87(H87A,H87B,H87C), C24(H24A,H24B,H24C), C64(H64A,H64B,H64C), C131(H13A,H13B,
 H13C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'