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_7063953
_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_absolute_configuration ad
_chemical_formula_moiety         'C33 H33 N O P, Br, 0.5(H2 O), C2 H6 O'
_chemical_formula_sum            'C35 H40 Br N O2.5 P'
_chemical_formula_weight         625.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.571(4)
_cell_length_b                   10.295(2)
_cell_length_c                   34.089(7)
_cell_measurement_reflns_used    9071
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      24.64
_cell_measurement_theta_min      2.29
_cell_volume                     6166(2)
_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      150.00
_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  0.1278
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            101874
_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         25.995
_diffrn_reflns_theta_min         2.066
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.419
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.5484
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1611 before and 0.0875 after correction.
The Ratio of minimum to maximum transmission is 0.7351.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       plate
_exptl_crystal_F_000             2616
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.142
_refine_diff_density_max         1.356
_refine_diff_density_min         -0.926
_refine_diff_density_rms         0.162
_refine_ls_abs_structure_details
;
 Refined as a perfect inversion twin.
;
_refine_ls_abs_structure_Flack   0.5
_refine_ls_extinction_coef       0.0136(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         12109
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.1002
_refine_ls_R_factor_gt           0.0871
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0969P)^2^+34.9721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2213
_refine_ls_wR_factor_ref         0.2296
_reflns_Friedel_coverage         0.965
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                10386
_reflns_number_total             12109
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj02552d2.cif
_cod_data_source_block           dp304_0m
_cod_depositor_comments
'Adding full bibliography for 7063950--7063958.cif.'
_cod_original_cell_volume        6167(2)
_cod_original_formula_sum        'C35 H40 Br N O2.50 P'
_cod_database_code               7063953
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.555
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 H3A-Br2
 2.4 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C31) = Uanis(C5)
4.a Free rotating group:
 O2(H2C,H2D)
4.b Ternary CH refined with riding coordinates:
 C1(H1), C58(H58), C9(H9), C66(H66)
4.c Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C56(H56A,H56B), C65(H65A,H65B), C67(H67A,H67B), C5(H5A,H5B),
 C17(H17A,H17B), C31(H31A,H31B), C61(H61A,H61B), C2(H2A,H2B), C7(H7A,H7B)
4.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C15(H15), C18(H18), C19(H19), C21(H21), C30(H30), C36(H36), C41(H41),
 C42(H42), C46(H46), C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
  C55(H55), C57(H57), C64(H64), C70(H70), C3(H3), C8(H8), C11(H11), C14(H14),
 C16(H16), C20(H20), C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C40(H40),
  C43(H43), C44(H44), C45(H45), C47(H47), C49(H49), C59(H59), C60(H60), C68(H68)
4.e Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C13(H13A,H13B,H13C), C63(H63A,H63B,H63C), C69(H69A,H69B,
 H69C)
4.f Idealised tetrahedral OH refined as rotating group:
 O3(H3A), O4(H4A)
;
_shelx_res_checksum              37350
_olex2_submission_special_instructions 'No special instructions were received'