Copper-Catalyzed spirocyclization-oxytrifluoromethylation of alkynyl-bicyclo[1.1.0]butanes for spirobutyl quinolones synthesis
Xu, Peng-Cheng; Xu, Yin; Wang, Yu-Ting; Mao, Jia Ling; Teng, Xu; Zhao, Yu Yang; Zou, Xiao; Yan, Shenghu; Jia, Zheng Ren; Zuo, Hang-Dong; Chemical Communications  (2026) –; doi:10.1039/D6CC00749J

data_7135627
_publ_section_title
;
 Copper-catalyzed spirocyclization-oxytrifluoromethylation of
 alkynyl-bicyclo[1.1.0]butanes for spirobutyl quinolone synthesis.
;
_journal_issue                   27
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7140
_journal_page_last               7144
_journal_paper_doi               10.1039/d6cc00749j
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C35 H27 F3 I N O3'
_chemical_formula_sum            'C35 H27 F3 I N O3'
_chemical_formula_weight         693.47
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-11-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-26 deposited with the CCDC.	2026-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.0963(5)
_cell_length_b                   9.7509(2)
_cell_length_c                   26.7974(6)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      68.22
_cell_measurement_theta_min      3.30
_cell_volume                     6035.0(2)
_computing_cell_refinement       'SAINT V8.41 (Bruker, 2024)'
_computing_data_collection       'APEX6 V2024.9-1 (Bruker, 2025)'
_computing_data_reduction        'SAINT V8.41 (Bruker, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2025/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III-M14'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f shutterless scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_monochromator  'Helios Multi-layer Optic'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            49730
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.335
_diffrn_reflns_theta_min         3.814
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec I\ms DIAMOND'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.808
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1020 before and 0.0571 after correction.
The Ratio of minimum to maximum transmission is 0.6394.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       block
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         5528
_refine_ls_number_restraints     549
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0413
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0473P)^2^+7.9456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1059
_refine_ls_wR_factor_ref         0.1094
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4801
_reflns_number_total             5528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00749j2.cif
_cod_data_source_block           a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7135627.cif.
;
_cod_original_sg_symbol_H-M      Pbca
_cod_database_code               7135627
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_max   0.539
_shelx_estimated_absorpt_t_min   0.394
_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
 C6A-C1A = C6A-C5A = C5A-C4A = C4A-C3A = C3A-C2A = C2A-C1A
 1.39 with sigma of 0.01
 O1-C8 \\sim O2A-C8
 with sigma of 0.02
 C24A-C23 \\sim C26A-C23 \\sim C24-C23 \\sim C26-C23
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim I1A \\sim F1A \\sim F2A \\sim F3A \\sim O1A \\sim
O2A \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim
C24A \\sim C25A \\sim C26A \\sim C27A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
I1 \\sim O1 \\sim O2 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6
\\sim C7 \\sim I1A \\sim O1A \\sim O2A \\sim C1A \\sim C2A \\sim C3A \\sim C4A
\\sim C5A \\sim C6A \\sim C7A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
F1 \\sim F2 \\sim F3 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim F1A \\sim
F2A \\sim F3A \\sim C24A \\sim C25A \\sim C26A \\sim C27A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{F1A, F2A, F3A, C24A, C25A, C26A, C27A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{F1, F2, F3, C24, C25, C26, C27}
{I1A, O1A, O2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.01, 1-3:
0.02
as in
{I1, O1, O2, C1, C2, C3, C4, C5, C6, C7}
5. Others
 Sof(I1A)=Sof(O1A)=Sof(O2A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=
 Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=1-FVAR(1)
 Sof(I1)=Sof(O1)=Sof(O2)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C25A(H25A)
6.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C24(H24A,H24B), C26(H26A,H26B), C24A(H24C,H24D), C26A(H26C,
 H26D)
6.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18),
 C19(H19), C20(H20), C30(H30), C31(H31), C33(H33), C34(H34), C2(H2), C3(H3),
 C4(H4), C5(H5), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A)
6.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C)
;
_shelx_res_checksum              2589
_shelx_hkl_checksum              5741
_olex2_submission_special_instructions 'No special instructions were received'
_site                            XU