"Trading" a C[double bond, length as m-dash]C moiety for four C-O bonds and a peroxide: combining ozone and <i>O</i>-nucleophiles for peroxidative ring expansion of cycloalkenes into medium-sized 1,2-dioxacycloalkanes.
Budekhin, Roman A.; Fomenkov, Dmitri I.; Ustyuzhanin, Alexander O.; Sliguzova, Darya Yu; Skokova, Ksenia V.; Vil', Vera A.; Alabugin, Igor V.; Terent'ev, Alexander O.; Chemical science 16 (2025) 21806–21814; doi:10.1039/d5sc06768e

data_1576319
_publ_section_title
;
 "Trading" a C[double bond, length as m-dash]C moiety for four C-O bonds
 and a peroxide: combining ozone and <i>O</i>-nucleophiles for
 peroxidative ring expansion of cycloalkenes into medium-sized
 1,2-dioxacycloalkanes.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              21806
_journal_page_last               21814
_journal_paper_doi               10.1039/d5sc06768e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C14 H20 O5'
_chemical_formula_sum            'C14 H20 O5'
_chemical_formula_weight         268.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-04-29
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2025-08-27 deposited with the CCDC.	2025-10-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.53370(10)
_cell_length_b                   11.12850(10)
_cell_length_c                   28.2876(3)
_cell_measurement_reflns_used    22373
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.4720
_cell_measurement_theta_min      3.1560
_cell_volume                     2666.19(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.117a 64-bit (release 26-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.117a (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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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   -119.00 -32.00   0.50    0.30    --  -48.17 -64.00 -71.00  174
  2  \w    -64.00  24.00   0.50    0.30    --  -48.17  64.00  64.00  176
  3  \w    -23.00  65.00   0.50    0.30    --   48.17 -64.00 -71.00  176
  4  \w   -161.00 -73.00   0.50    1.50    --  -90.00 -64.00 -71.00  176
  5  \w    -76.00 -18.00   0.50    1.50    --  -90.00  64.00  64.00  116
  6  \w    135.00 178.00   0.50    1.50    --  111.50  64.00  64.00   86
  7  \w     97.00 130.00   0.50    1.50    --  111.50  64.00  64.00   66
  8  \w     41.00  67.00   0.50    1.50    --  111.50 -64.00 -71.00   52
  9  \w    -84.00 -13.00   0.50    0.30    --  -48.17 125.00-180.00  142
 10  \w     52.00  77.00   0.50    0.30    --   48.17  64.00  64.00   50
 11  \w    -49.00 -22.00   0.50    1.50    --  -90.00  45.00-120.00   54
 12  \w    -47.00 -22.00   0.50    1.50    --  -90.00  45.00 -90.00   50
 13  \w     58.00 104.00   0.50    1.50    --  111.50 -77.00  90.00   92
 14  \w     40.00  70.00   0.50    1.50    --  111.50 -61.00-150.00   60
 15  \w     41.00  71.00   0.50    1.50    --  111.50 -61.00 150.00   60
 16  \w    102.00 146.00   0.50    1.50    --  111.50  15.00-180.00   88
 17  \w    152.00 177.00   0.50    1.50    --  111.50  30.00   0.00   50
 18  \w     79.00 105.00   0.50    1.50    --  111.50 -77.00  30.00   52
 19  \w    150.00 175.00   0.50    1.50    --  111.50  45.00 -90.00   50
 20  \w     74.00 103.00   0.50    1.50    --  111.50 -77.00 -30.00   58
 21  \w     59.00  85.00   0.50    1.50    --  111.50 -77.00-150.00   52
 22  \w    127.00 177.00   0.50    1.50    --  111.50  30.00  30.00  100
 23  \w     41.00 102.00   0.50    1.50    --  111.50 -77.00-180.00  122
 24  \w    108.00 151.00   0.50    1.50    --  111.50  61.00  90.00   86
 25  \w     40.00  70.00   0.50    1.50    --  111.50 -61.00  90.00   60
 26  \w    105.00 177.00   0.50    1.50    --  111.50  45.00 -30.00  144
 27  \w    101.00 156.00   0.50    1.50    --  111.50  30.00-150.00  110
 28  \w     40.00  88.00   0.50    1.50    --  111.50 -95.00   0.00   96
 29  \w     44.00  70.00   0.50    1.50    --  111.50 -61.00 -60.00   52
 30  \w    101.00 132.00   0.50    1.50    --  111.50  45.00 -90.00   62
 31  \w    138.00 165.00   0.50    1.50    --  111.50  77.00  30.00   54
 32  \w    102.00 147.00   0.50    1.50    --  111.50  15.00  30.00   90
 33  \w     41.00  67.00   0.50    1.50    --  111.50 -77.00   0.00   52
 34  \w     71.00 101.00   0.50    1.50    --  111.50 -77.00   0.00   60
 35  \w    106.00 172.00   0.50    1.50    --  111.50  45.00 -60.00  132
 36  \w    108.00 140.00   0.50    1.50    --  111.50  30.00  60.00   64
 37  \w    143.00 174.00   0.50    1.50    --  111.50  30.00  60.00   62
 38  \w     96.00 123.00   0.50    1.50    --  111.50  77.00  30.00   54
 39  \w     41.00  70.00   0.50    1.50    --  111.50 -61.00-120.00   58
 40  \w     40.00  65.00   0.50    1.50    --  111.50 -61.00   0.00   50
 41  \w    124.00 175.00   0.50    1.50    --  111.50  45.00-150.00  102
 42  \w    102.00 143.00   0.50    1.50    --  111.50  45.00  30.00   82
 43  \w    134.00 160.00   0.50    1.50    --  111.50  30.00-180.00   52
 44  \w     53.00  78.00   0.50    1.50    --  111.50   0.00-180.00   50
 45  \w     92.00 118.00   0.50    1.50    --  111.50   0.00-180.00   52
 46  \w     50.00  88.00   0.50    1.50    --  111.50 -95.00-120.00   76
 47  \w     56.00  82.00   0.50    1.50    --  111.50 -95.00  90.00   52
 48  \w     53.00  79.00   0.50    1.50    --  111.50-125.00  30.00   52
 49  \w     85.00 111.00   0.50    1.50    --  111.50-125.00  30.00   52
 50  \w    126.00 152.00   0.50    1.50    --  111.50 125.00 -30.00   52
 51  \w    122.00 164.00   0.50    1.50    --  111.50 125.00  90.00   84
 52  \w     46.00  82.00   0.50    1.50    --  111.50-102.00-133.82   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0687524000
_diffrn_orient_matrix_UB_12      -0.1025799000
_diffrn_orient_matrix_UB_13      -0.0277010000
_diffrn_orient_matrix_UB_21      -0.1453799000
_diffrn_orient_matrix_UB_22      0.0057051000
_diffrn_orient_matrix_UB_23      -0.0380112000
_diffrn_orient_matrix_UB_31      0.0849174000
_diffrn_orient_matrix_UB_32      0.0927847000
_diffrn_orient_matrix_UB_33      -0.0282811000
_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  0.0291
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            35256
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.826
_diffrn_reflns_theta_min         3.148
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.838
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.203
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.117a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.39
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5748
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0487P)^2^+1.9139P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1100
_refine_ls_wR_factor_ref         0.1116
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5337
_reflns_number_total             5748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06768e4.cif
_cod_data_source_block           rp-463
_cod_original_cell_volume        2666.20(5)
_cod_database_code               1576319
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C14H20O5
_chemical_oxdiff_usercomment     RP-463
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.709
_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.a Ternary CH refined with riding coordinates:
 C1(H1A), C5(H5), C15(H15), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C22(H22), C23(H23), C24(H24),
 C25(H25), C26(H26)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C)
;
_shelx_res_checksum              3464
_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 1.222
_oxdiff_exptl_absorpt_empirical_full_min 0.811