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_7160966
_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_absolute_configuration ad
_chemical_formula_moiety         'C25 H31 N O6 S'
_chemical_formula_sum            'C25 H31 N O6 S'
_chemical_formula_weight         473.57
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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                93.60(2)
_cell_angle_beta                 93.791(15)
_cell_angle_gamma                90.125(10)
_cell_formula_units_Z            2
_cell_length_a                   8.7430(15)
_cell_length_b                   9.576(4)
_cell_length_c                   14.697(3)
_cell_measurement_reflns_used    9867
_cell_measurement_temperature    220(2)
_cell_measurement_theta_max      72.21
_cell_measurement_theta_min      5.73
_cell_volume                     1225.3(6)
_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      220.0
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_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  0.0569
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            31493
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        66.974
_diffrn_reflns_theta_max         66.974
_diffrn_reflns_theta_min         4.627
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.507
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.4683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1383 before and 0.0924 after correction. The Ratio of minimum to maximum transmission is 0.6003. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       prism
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.738
_refine_diff_density_min         -0.658
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         8290
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0509
_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^)+(0.0922P)^2^+0.5251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.913
_reflns_Friedel_fraction_max     0.913
_reflns_number_gt                8001
_reflns_number_total             8290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00091f2.cif
_cod_data_source_block           sto775c_0m_a
_cod_depositor_comments
'Adding full bibliography for 7160965--7160966.cif.'
_cod_database_code               7160966
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.661
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.93(2)
 0.07(2)
2. 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
3. Uiso/Uaniso restraints and constraints
Uanis(C49) = Uanis(C24)
Uanis(C50) = Uanis(C25)
4.a Ternary CH refined with riding coordinates:
 C32(H32), C7(H7)
4.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C47(H47A,H47B), C20(H20A,H20B), C48(H48A,H48B), C23(H23A,
 H23B), C42(H42A,H42B), C17(H17A,H17B), C49(H49A,H49B), C45(H45A,H45B),
 C24(H24A,H24B)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C2(H2), C3(H3), C28(H28), C5(H5), C35(H35), C14(H14), C4(H4),
 C39(H39), C10(H10), C30(H30), C13(H13), C29(H29), C11(H11), C36(H36), C38(H38)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C40(H40A,H40B,H40C), C18(H18A,H18B,H18C), C50(H50A,H50B,
 H50C), C46(H46A,H46B,H46C), C43(H43A,H43B,H43C), C21(H21A,H21B,H21C), C25(H25A,
 H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'