Synthesis of fluorine-containing bicyclo[4.1.1]octenes <i>via</i> photocatalyzed defluorinative (4 + 3) annulation of bicyclo[1.1.0]butanes with <i>gem</i>-difluoroalkenes.
Zhang, Kuan; Gao, Zhengyang; Xia, Yan; Li, Pengfei; Gao, Pin; Duan, Xin-Hua; Guo, Li-Na; Chemical science 16 (2025) 1411–1416; doi:10.1039/d4sc07243j

data_1573465
_publ_section_title
;
 Synthesis of fluorine-containing bicyclo[4.1.1]octenes <i>via</i>
 photocatalyzed defluorinative (4 + 3) annulation of bicyclo[1.1.0]butanes
 with <i>gem</i>-difluoroalkenes.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1411
_journal_page_last               1416
_journal_paper_doi               10.1039/d4sc07243j
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H19 F O2'
_chemical_formula_sum            'C22 H19 F O2'
_chemical_formula_weight         334.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-06 deposited with the CCDC.	2024-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4103(2)
_cell_length_b                   16.6264(3)
_cell_length_c                   9.23370(10)
_cell_measurement_reflns_used    6141
_cell_measurement_temperature    301.00
_cell_measurement_theta_max      68.168
_cell_measurement_theta_min      3.874
_cell_volume                     1751.75(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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      301.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0336
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            12016
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.253
_diffrn_reflns_theta_min         4.700
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.707
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6437
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1220 before and 0.0573 after correction.
The Ratio of minimum to maximum transmission is 0.8548.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.149
_refine_diff_density_min         -0.147
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1193 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.09(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3049
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0566P)^2^+0.1410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0949
_refine_ls_wR_factor_ref         0.0972
_reflns_Friedel_coverage         0.785
_reflns_Friedel_fraction_full    0.901
_reflns_Friedel_fraction_max     0.899
_reflns_number_gt                2880
_reflns_number_total             3049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07243j2.cif
_cod_data_source_block           5aa
_cod_depositor_comments
'Adding full bibliography for 1573464--1573465.cif.'
_cod_database_code               1573465
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
3. Rigid body (RIGU) restrains
 C17, C18, C19, C20, C21, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C4(H4)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C9(H9A,H9B), C10(H10A,H10B)
4.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22)
;
_shelx_res_checksum              35485
_shelx_hkl_checksum              56217
_olex2_submission_special_instructions 'No special instructions were received'