Organocatalytic regio-and stereoselective synthesis of chiral tetrasubstituted α-amino allenoates by γ-additions of β,γ-alkynylα-imino esters with pyrazolones
Zhou, Zhenghua; Xu, Yongqiang; Li, Wenkai; Qu, Jingping; Zhou, Yuhan; Wang, Baomin; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D6OB00191B

data_7161062
_publ_section_title
;
 Organocatalytic regio- and stereoselective synthesis of chiral
 tetrasubstituted &#x3b1;-amino allenoates by &#x3b3;-addition of
 &#x3b2;,&#x3b3;-alkynyl-&#x3b1;-imino esters with pyrazolones.
;
_journal_issue                   14
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2888
_journal_page_last               2892
_journal_paper_doi               10.1039/d6ob00191b
_journal_volume                  24
_journal_year                    2026
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C39 H36 Br N3 O5'
_chemical_formula_sum            'C39 H36 Br N3 O5'
_chemical_formula_weight         706.62
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2026-01-30 deposited with the CCDC.	2026-03-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3276(12)
_cell_length_b                   12.7751(17)
_cell_length_c                   29.524(4)
_cell_measurement_reflns_used    9091
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      23.25
_cell_measurement_theta_min      2.58
_cell_volume                     3518.1(8)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.1205
_diffrn_reflns_av_unetI/netI     0.0583
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            77053
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.734
_diffrn_reflns_theta_min         2.108
_diffrn_source_current           1.6
_diffrn_source_power             0.08
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.216
_exptl_absorpt_correction_T_max  0.7219
_exptl_absorpt_correction_T_min  0.6242
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1857 before and 0.1168 after correction.
The Ratio of minimum to maximum transmission is 0.8647.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.247
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 2055 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.016(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     441
_refine_ls_number_reflns         6718
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0554
_refine_ls_R_factor_gt           0.0383
_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^)+(0.0158P)^2^+1.1374P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0677
_refine_ls_wR_factor_ref         0.0753
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                5602
_reflns_number_total             6718
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00191b2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7161062.cif.'
_cod_database_code               7161062
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.811
_shelx_estimated_absorpt_t_min   0.793
_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:
 C00Q(H00B,H00D), C013(H01A,H01B)
2.b Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00C(H00C), C00G(H00G), C00J(H00J), C00K(H00K), C00P(H00P),
 C00T(H00T), C00U(H00U), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C012(H012), C014(H014), C015(H015), C017(H017),
 C01B(H01L)
2.c Idealised Me refined as rotating group:
 C018(H01C,H01D,H01E), C019(H01F,H01G,H01H), C01A(H01I,H01J,H01K), C01C(H01M,
 H01N,H01O)
;
_shelx_res_checksum              46517
_olex2_submission_special_instructions 'No special instructions were received'