From alkynes to spiroindole δ-lactams via a copper-nitrenoid intermediate featuring unusual 1,1-addition and high Z-selectivity
Ren, Zhiqiang; Feng, Tianhui; Li, Yeyao; Chu, Mengyi; Zheng, Ye; Gao, Tianli; Han, Bo; Guo, Ruili; Ma, Haojie; Wang, Ji-Jiang; Zhang, Yuqi; Chemical Science  (2026) –; doi:10.1039/D5SC09742H

data_1577000
_publ_section_title
;
 From alkynes to spiroindole &#x3b4;-lactams <i>via</i> a copper-nitrenoid
 intermediate featuring unusual 1,1-addition and high
 <i>Z</i>-selectivity.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              9695
_journal_page_last               9702
_journal_paper_doi               10.1039/d5sc09742h
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C22 H29 N3 O2'
_chemical_formula_sum            'C22 H29 N3 O2'
_chemical_formula_weight         367.48
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-06-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-08-11 deposited with the CCDC.	2026-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                100.8520(10)
_cell_angle_beta                 94.3000(10)
_cell_angle_gamma                107.0780(10)
_cell_formula_units_Z            2
_cell_length_a                   7.6565(2)
_cell_length_b                   10.3732(3)
_cell_length_c                   14.0443(4)
_cell_measurement_reflns_used    9933
_cell_measurement_temperature    213.00
_cell_measurement_theta_max      66.61
_cell_measurement_theta_min      4.99
_cell_volume                     1037.05(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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      213.00
_diffrn_measured_fraction_theta_full 0.960
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.960
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            13312
_diffrn_reflns_point_group_measured_fraction_full 0.960
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        66.702
_diffrn_reflns_theta_max         66.702
_diffrn_reflns_theta_min         6.162
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.602
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6742
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0556 before and 0.0380 after correction.
The Ratio of minimum to maximum transmission is 0.8956.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       block
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.026
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3518
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0457P)^2^+0.2664P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3344
_reflns_number_total             3518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09742h3.cif
_cod_data_source_block           a_a
_cod_depositor_comments
'Adding full bibliography for 1577000--1577003.cif.'
_cod_database_code               1577000
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.931
_olex2_refinement_description
;
1. Restrained distances
 C19-C15 \\sim C18-C15
 with sigma of 0.02
 C23-C20 \\sim C22-C20
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C16 \\sim C18 \\sim C19: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
3.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C15(H15A,H15B), C20(H20A,H20B)
3.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C13(H13)
3.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C)
;
_shelx_res_checksum              14491
_olex2_submission_special_instructions 'No special instructions were received'