Synthesis of α-trifluoromethyl-β-lactams <i>via</i> a copper-catalyzed Kinugasa reaction of nitrones with 3,3,3-trifluoropropyne and their defluorination.
Chen, Shouxiong; Yang, Peiqi; Hong, Biqiong; Yang, Fafu; Weng, Zhiqiang; Organic & biomolecular chemistry 24 (2026) 1908–1914; doi:10.1039/d5ob01913c

data_7160944
_publ_section_title
;
 Synthesis of &#x3b1;-trifluoromethyl-&#x3b2;-lactams <i>via</i> a
 copper-catalyzed Kinugasa reaction of nitrones with
 3,3,3-trifluoropropyne and their defluorination.
;
_journal_issue                   9
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1908
_journal_page_last               1914
_journal_paper_doi               10.1039/d5ob01913c
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         '2(C15 H17 F4 N O S)'
_chemical_formula_sum            'C30 H34 F8 N2 O2 S2'
_chemical_formula_weight         670.71
_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_block_doi                 10.5517/ccdc.csd.cc2pbslf
_audit_creation_date             2025-08-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-08-27 deposited with the CCDC.	2026-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                74.955(5)
_cell_angle_beta                 69.286(6)
_cell_angle_gamma                63.657(6)
_cell_formula_units_Z            2
_cell_length_a                   11.0610(7)
_cell_length_b                   12.0662(8)
_cell_length_c                   15.1287(9)
_cell_measurement_reflns_used    5346
_cell_measurement_temperature    298
_cell_measurement_theta_max      24.6590
_cell_measurement_theta_min      2.4290
_cell_volume                     1679.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -31.00  77.00   0.50    6.46    --   -9.10  29.00 -60.00  216
  2  \w    -12.00  80.00   0.50    6.46    --   -9.10  55.00-180.00  184
  3  \w    -85.00 -60.00   0.50    6.46    --   -9.10  55.00  60.00   50
  4  \w    -29.00  75.00   0.50    6.46    --   -9.10  55.00  60.00  208
  5  \w    -80.00 -52.00   0.50    6.46    --   -9.10  55.00 -60.00   56
  6  \w    -19.00  73.00   0.50    6.46    --   -9.10  55.00 -60.00  184
  7  \w    -90.00 -65.00   0.50    6.46    --   -9.10  55.00  90.00   50
  8  \w     24.00  49.00   0.50    6.46    --   -9.10  55.00  90.00   50
  9  \w    -79.00 -49.00   0.50    6.46    --   -9.10  29.00 -60.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0170321000
_diffrn_orient_matrix_UB_12      -0.0524251000
_diffrn_orient_matrix_UB_13      0.0071661000
_diffrn_orient_matrix_UB_21      -0.0057233000
_diffrn_orient_matrix_UB_22      0.0138211000
_diffrn_orient_matrix_UB_23      -0.0472286000
_diffrn_orient_matrix_UB_31      0.0722390000
_diffrn_orient_matrix_UB_32      -0.0378008000
_diffrn_orient_matrix_UB_33      -0.0163954000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20514
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.175
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.232
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.326
_exptl_crystal_description       plate
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.672
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         5903
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0804
_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^)+(0.1780P)^2^+0.5159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2508
_refine_ls_wR_factor_ref         0.2726
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4219
_reflns_number_total             5903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01913c2.cif
_cod_data_source_block           ysh-4-20250729
_cod_depositor_comments
'Adding full bibliography for 7160944--7160947.cif.'
_cod_database_code               7160944
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.989
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 S001-C17 = S1-C15
 1.74 with sigma of 0.001
3. Rigid bond restraints
 S001, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 S1, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C016, F6
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C15) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8) \\sim Ueq, Uanis(C013) \\sim Ueq, Uanis(C016) \\sim Ueq, Uanis(C014)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C013) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(S1) \\sim Ueq, Uanis(S001) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F6) \\sim Ueq, Uanis(C016) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: C17(0.5) H17A(0.5) H17B(0.5) C16(0.5) H16A(0.5) H16B(0.5) F5(0.5)
 F6(0.5)
6.a Ternary CH refined with riding coordinates:
 C00D(H00D), C4(H4), C00O(H00O), C2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C17(H17A,H17B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C00L(H00L), C00N(H00N), C13(H13), C00Q(H00Q), C10(H10), C00T(H00T),
 C11(H11)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C013(H01A,H01B,H01C),
 C014(H01D,H01E,H01F), C016(H01G,H01H,H01I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              89357
_shelx_fab_checksum              96292
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.732
_oxdiff_exptl_absorpt_empirical_full_min 0.705