Diastereospecific cyclization of 3-arylidene-1-pyrrolinium salts containing an alkyltriarylphosphonium fragment: a path to the synthesis of new pyrrolizidine derivatives
Rizbayeva, Tanzilya; Smolobochkin, Andrey; Gazizov, Almir; Babaeva, Olga; Lyubina, Anna; Sapunova, Anastasiia; Voloshina, Alexandra; Gerasimova, Daria; Burilov, Alexander; Pudovik, Michail; New Journal of Chemistry 49 (2025) 14718–14727; doi:10.1039/D5NJ02552D

data_7063950
_publ_section_title
;
 Diastereospecific cyclization of 3-arylidene-1-pyrrolinium salts
 containing an alkyltriarylphosphonium fragment: a path to the synthesis
 of new pyrrolizidine derivatives
;
_journal_issue                   34
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              14718
_journal_page_last               14727
_journal_paper_doi               10.1039/D5NJ02552D
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C32 H30 Cl N P, Br, C3 H6 O1'
_chemical_formula_sum            'C35 H36 Br Cl N O P'
_chemical_formula_weight         632.98
_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             2024-12-17
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-17 deposited with the CCDC.	2025-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                106.349(4)
_cell_angle_beta                 103.089(5)
_cell_angle_gamma                102.213(5)
_cell_formula_units_Z            2
_cell_length_a                   10.4277(18)
_cell_length_b                   12.208(2)
_cell_length_c                   14.862(3)
_cell_measurement_reflns_used    9920
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      29.96
_cell_measurement_theta_min      2.18
_cell_volume                     1689.8(5)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            56123
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.999
_diffrn_reflns_theta_min         1.916
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.369
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.4857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1107 before and 0.0648 after correction.
The Ratio of minimum to maximum transmission is 0.6511.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       prism
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.594
_exptl_crystal_size_mid          0.458
_exptl_crystal_size_min          0.397
_refine_diff_density_max         1.009
_refine_diff_density_min         -0.698
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         7379
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0502P)^2^+1.3773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6254
_reflns_number_total             7379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj02552d2.cif
_cod_data_source_block           dp273_0m
_cod_depositor_comments
'Adding full bibliography for 7063950--7063958.cif.'
_cod_original_cell_volume        1689.9(5)
_cod_database_code               7063950
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.613
_shelx_estimated_absorpt_t_min   0.497
_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. Restrained distances
 O17-C2 \\sim O17A-C2A
 with sigma of 0.02
 C2-C33 \\sim C2A-C33A
 with sigma of 0.02
 C2-C36 \\sim C2A-C36A
 with sigma of 0.02
 O17-C33 \\sim O17A-C33A
 with sigma of 0.04
 O17-C36 \\sim O17A-C36A
 with sigma of 0.04
 C33-C36 \\sim C33A-C36A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C36A) = Uanis(C33A) = Uanis(C2) = Uanis(C36) = Uanis(C2A) = Uanis(C33)
Uanis(O17A) = Uanis(O17)
4. Others
 Sof(O17A)=Sof(C2A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C36A)=
 Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(O17)=Sof(C2)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C19(H19A,H19B), C26(H26A,H26B), C35(H35A,H35B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C12(H12), C13(H13), C15(H15), C16(H16), C18(H18),
 C20(H20), C21(H21), C23(H23), C24(H24), C25(H25), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), C32(H32), C34(H34)
5.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C36(H36A,H36B,H36C), C33A(H33D,H33E,H33F), C36A(H36D,
 H36E,H36F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26968
_shelx_fab_checksum              1046
_olex2_submission_special_instructions 'No special instructions were received'