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_1577002
_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         'C31 H39 Cu N2 O2'
_chemical_formula_sum            'C31 H39 Cu N2 O2'
_chemical_formula_weight         535.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-10-29 deposited with the CCDC.	2026-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.773(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4903(7)
_cell_length_b                   12.6689(7)
_cell_length_c                   22.1306(11)
_cell_measurement_reflns_used    9832
_cell_measurement_temperature    223.00
_cell_measurement_theta_max      68.39
_cell_measurement_theta_min      4.02
_cell_volume                     3501.6(3)
_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      223.00
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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  0.0415
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            27534
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        66.590
_diffrn_reflns_theta_max         66.590
_diffrn_reflns_theta_min         4.021
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.055
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5613
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1028 before and 0.0679 after correction.
The Ratio of minimum to maximum transmission is 0.7453.
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    1.015
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.804
_refine_diff_density_min         -0.887
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         6111
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.1052
_refine_ls_R_factor_gt           0.1019
_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^)+(0.3500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3720
_refine_ls_wR_factor_ref         0.3873
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5546
_reflns_number_total             6111
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09742h3.cif
_cod_data_source_block           a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1577000--1577003.cif.'
_cod_database_code               1577002
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.858
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C17 \\sim C19 \\sim C18: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C29 \\sim C30 \\sim C31: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
2.a Riding coordinates:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C19(H19A,H19B,
 H19C), C18(H18A,H18B,H18C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C)
2.b Ternary CH refined with riding coordinates:
 C17(H17), C14(H14), C29(H29), C26(H26)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C24(H24), C23(H23), C22(H22)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              67869
_shelx_fab_checksum              73680
_olex2_submission_special_instructions 'No special instructions were received'