Enantioselective copper(II) catalysed (4 + 1) cycloaddition of aza-<i>o</i>-quinone methides and bromomalonates. Facile access to enantioenriched indolines.
Torres-Oya, Sergio; Fernández-Rodríguez, Manuel A; Zurro, Mercedes; Organic & biomolecular chemistry 24 (2026) 1690–1696; doi:10.1039/d6ob00091f

data_7160965
_publ_section_title
;
 Enantioselective copper(II) catalysed (4 + 1) cycloaddition of
 aza-<i>o</i>-quinone methides and bromomalonates. Facile access to
 enantioenriched indolines.
;
_journal_issue                   8
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1690
_journal_page_last               1696
_journal_paper_doi               10.1039/d6ob00091f
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C27 H26 F N O6 S'
_chemical_formula_sum            'C27 H26 F N O6 S'
_chemical_formula_weight         511.55
_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             2025-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-08-07 deposited with the CCDC.	2026-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                66.33(4)
_cell_angle_beta                 89.21(3)
_cell_angle_gamma                71.32(3)
_cell_formula_units_Z            2
_cell_length_a                   8.532(6)
_cell_length_b                   12.602(7)
_cell_length_c                   13.827(7)
_cell_measurement_reflns_used    8147
_cell_measurement_temperature    299(2)
_cell_measurement_theta_max      72.13
_cell_measurement_theta_min      3.52
_cell_volume                     1278.5(14)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      299.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            37546
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.503
_diffrn_reflns_theta_min         3.521
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.550
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5902
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1129 before and 0.0747 after correction. The Ratio of minimum to maximum transmission is 0.7832. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       neddle
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.032
_refine_diff_density_min         -1.070
_refine_diff_density_rms         0.069
_refine_ls_extinction_coef       0.009(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         5024
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1097
_refine_ls_R_factor_gt           0.0847
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1595P)^2^+0.9347P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2431
_refine_ls_wR_factor_ref         0.2805
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3595
_reflns_number_total             5024
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00091f2.cif
_cod_data_source_block           sto709f1b_0m_a
_cod_depositor_comments
'Adding full bibliography for 7160965--7160966.cif.'
_cod_original_cell_volume        1278.6(14)
_cod_database_code               7160965
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.698
_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
 C26-C27
 1.44 with sigma of 0.02
3. Rigid bond restraints
 C26, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C26) = Uanis(C23)
Uanis(C27) = Uanis(C24)
5.a Ternary CH refined with riding coordinates:
 C7(H7)
5.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C26(H26A,H26B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C20(H20), C5(H5), C19(H19), C16(H16), C4(H4), C14(H14), C10(H10),
 C17(H17), C13(H13), C11(H11), C12(H12)
5.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C21(H21A,H21B,H21C), C27(H27A,H27B,H27C)
;
_olex2_submission_special_instructions 'No special instructions were received'