Organo-catalyzed photoelectrochemical ring-contraction of arylidenecyclobutanols via radical cation-triggered semipinacol rearrangement
Zheng, Yu; Chen, Chunxi; Zhou, Xuhao; Deng, Guoyang; Lu, Yanju; Huang, Shenlin; Chemical Science  (2025) –; doi:10.1039/D5SC07637D

data_1576348
_publ_section_title
;
 Organo-catalyzed photoelectrochemical ring-contraction of
 arylidenecyclobutanols via radical cation-triggered semipinacol
 rearrangement
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07637D
_journal_year                    2025
_chemical_formula_moiety         'C11 H10 O3'
_chemical_formula_sum            'C11 H10 O3'
_chemical_formula_weight         190.19
_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_block_doi                 10.5517/ccdc.csd.cc2nfg2n
_audit_creation_date             2024-10-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-02 deposited with the CCDC.	2025-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.6635(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2361(2)
_cell_length_b                   5.83641(11)
_cell_length_c                   13.4714(3)
_cell_measurement_reflns_used    4083
_cell_measurement_temperature    298.41(10)
_cell_measurement_theta_max      72.7980
_cell_measurement_theta_min      5.1900
_cell_volume                     955.56(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.41(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.963
_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     56.00 101.00   0.50    0.10    --   62.58  15.00 150.00   90
  2  \w     57.00  92.00   0.50    0.10    --   62.58  15.00  60.00   70
  3  \w     64.00 103.00   0.50    0.10    --   62.58  15.00   0.00   78
  4  \w     78.00 103.00   0.50    0.10    --   74.47  15.00  90.00   50
  5  \w     81.00 111.00   0.50    0.10    --   71.33  15.00   0.00   60
  6  \w     86.00 111.00   0.50    0.10    --   74.47  15.00 -30.00   50
  7  \w     55.00  86.00   0.50    0.10    --   62.58  15.00 -30.00   62
  8  \w     69.00  94.00   0.50    0.10    --   74.47  15.00  30.00   50
  9  \w     82.00 107.00   0.50    0.10    --   74.47  15.00  60.00   50
 10  \w     67.00  98.00   0.50    0.10    --   74.47  15.00 150.00   62
 11  \w     69.00  97.00   0.50    0.10    --   74.47  15.00 -60.00   56
 12  \w     56.00  99.00   0.50    0.10    --   62.58  15.00 -90.00   86
 13  \w     78.00 112.00   0.50    0.10    --   74.47  15.00-150.00   68
 14  \w     73.00  99.00   0.50    0.10    --   74.47  15.00-180.00   52
 15  \w     42.00  67.00   0.50    0.10    --   74.47-125.00 -90.00   50
 16  \w     27.00  56.00   0.50    0.10    --   62.58-125.00 -90.00   58
 17  \w     44.00  70.00   0.50    0.10    --   62.58-125.00-120.00   52
 18  \w     26.00  59.00   0.50    0.10    --   62.58-125.00-180.00   66
 19  \w     39.00  78.00   0.50    0.10    --   71.33-125.00-180.00   78
 20  \w     42.00  67.00   0.50    0.10    --   74.47-125.00-120.00   50
 21  \w     45.00  70.00   0.50    0.10    --   62.58-125.00  60.00   50
 22  \w     58.00  85.00   0.50    0.10    --   74.47-125.00 120.00   54
 23  \w     37.00  63.00   0.50    0.10    --   62.58-125.00 150.00   52
 24  \w     45.00  71.00   0.50    0.10    --   74.47-125.00 150.00   52
 25  \w     52.00  89.00   0.50    0.10    --   74.47-125.00-150.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0878390000
_diffrn_orient_matrix_UB_12      0.0528451000
_diffrn_orient_matrix_UB_13      -0.0886342000
_diffrn_orient_matrix_UB_21      0.0814374000
_diffrn_orient_matrix_UB_22      -0.0707741000
_diffrn_orient_matrix_UB_23      -0.0735114000
_diffrn_orient_matrix_UB_31      -0.0415427000
_diffrn_orient_matrix_UB_32      -0.2486522000
_diffrn_orient_matrix_UB_33      0.0020683000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0126
_diffrn_reflns_av_unetI/netI     0.0130
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5904
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.894
_diffrn_reflns_theta_min         4.623
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.798
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90218
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
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    1.322
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.143
_refine_diff_density_min         -0.129
_refine_diff_density_rms         0.029
_refine_ls_extinction_coef       0.0054(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     132
_refine_ls_number_reflns         1834
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0350
_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^)+(0.0562P)^2^+0.1026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1047
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1600
_reflns_number_total             1834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07637d2.cif
_cod_data_source_block           ccx-1_auto
_cod_original_cell_volume        955.55(3)
_cod_database_code               1576348
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.903
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C11(H11), C9(H9), C8(H8), C10(H10)
;
_shelx_res_checksum              90829
_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 1.422
_oxdiff_exptl_absorpt_empirical_full_min 0.707