Visible light-induced 1,2-alkoxy shift of α-diazoacetates for Wolff rearrangements - access to oxyketenes.
Liu, Yang; Xie, Zi-Yi; Kloene, Lennard; Xu, Cong-Lun; Tai, Jian-Peng; Zhu, Yu; Cai, Bao-Gui; Pan, Chongqing; Koenigs, Rene M.; Xuan, Jun; Chemical science 17 (2026) 3587–3592; doi:10.1039/d5sc08263c

data_1576598
_publ_section_title
;
 Visible light-induced 1,2-alkoxy shift of &#x3b1;-diazoacetates for Wolff
 rearrangements - access to oxyketenes.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              3587
_journal_page_last               3592
_journal_paper_doi               10.1039/d5sc08263c
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C23 H21 N O2'
_chemical_formula_sum            'C23 H21 N O2'
_chemical_formula_weight         343.41
_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_creation_date             2025-08-19
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-13 deposited with the CCDC.	2025-12-19 downloaded from the CCDC.
;
_cell_angle_alpha                84.919(2)
_cell_angle_beta                 71.480(3)
_cell_angle_gamma                75.360(2)
_cell_formula_units_Z            2
_cell_length_a                   8.5050(3)
_cell_length_b                   9.0705(2)
_cell_length_c                   13.1678(4)
_cell_measurement_reflns_used    7129
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.4610
_cell_measurement_theta_min      3.5210
_cell_volume                     931.91(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -65.00 -34.00   0.50    0.20    -- -105.00  61.00  90.00   62
  2  \w    -23.00   5.00   0.50    0.10    --  -46.65  19.00  90.00   56
  3  \w    -20.00  24.00   0.50    0.10    --  -46.65  19.00  30.00   88
  4  \w    -71.00 -34.00   0.50    0.20    -- -105.00  61.00 -60.00   74
  5  \w    -21.00   5.00   0.50    0.10    --  -46.65  19.00-120.00   52
  6  \w    -10.00  27.00   0.50    0.10    --   46.65 -19.00   0.00   74
  7  \w    -29.00  22.00   0.50    0.10    --   46.65 -19.00-180.00  102
  8  \w    126.00 152.00   0.50    0.20    --  108.03  83.00 100.00   52
  9  \w    -22.00  43.00   0.50    0.10    --   46.65 -38.00 120.00  130
 10  \w     44.00  79.00   0.50    0.20    --  108.03-125.00  60.00   70
 11  \w     87.00 112.00   0.50    0.20    --  108.03-125.00  60.00   50
 12  \w     66.00  91.00   0.50    0.20    --  108.03-125.00   0.00   50
 13  \w     45.00  71.00   0.50    0.20    --  108.03 -95.00 -30.00   52
 14  \w     78.00 103.00   0.50    0.20    --  108.03 -95.00 -30.00   50
 15  \w     35.00  72.00   0.50    0.20    --  108.03 -83.00 -20.00   74
 16  \w     -6.00  73.00   0.50    0.10    --   46.65 -83.00 -20.00  158
 17  \w     50.00 111.00   0.50    0.20    --  108.03-125.00-150.00  122
 18  \w     81.00 107.00   0.50    0.20    --  108.03-125.00-180.00   52
 19  \w     35.00  80.00   0.50    0.20    --  108.03 -95.00-150.00   90
 20  \w     36.00  68.00   0.50    0.20    --  108.03 -61.00-180.00   64
 21  \w     78.00 104.00   0.50    0.20    --  108.03 -77.00-180.00   52
 22  \w     37.00  67.00   0.50    0.20    --  108.03 -61.00-120.00   60
 23  \w     39.00  71.00   0.50    0.20    --  108.03 -61.00  60.00   64
 24  \w     35.00  71.00   0.50    0.20    --  108.03 -61.00 120.00   72
 25  \w    140.00 172.00   0.50    0.20    --  108.03  45.00  90.00   64
 26  \w    105.00 176.00   0.50    0.20    --  108.03  61.00 120.00  142
 27  \w    116.00 176.00   0.50    0.20    --  108.03  45.00 150.00  120
 28  \w     95.00 134.00   0.50    0.20    --  108.03  45.00  90.00   78
 29  \w     99.00 173.00   0.50    0.20    --  108.03  77.00-120.00  148
 30  \w    110.00 176.00   0.50    0.20    --  108.03  61.00-180.00  132
 31  \w    -46.00  19.00   0.50    0.10    --  -46.65  83.00 100.00  130
 32  \w   -109.00 -35.00   0.50    0.20    -- -105.00 125.00  30.00  148
 33  \w    -96.00 -45.00   0.50    0.20    -- -105.00  83.00 100.00  102
 34  \w   -139.00 -92.00   0.50    0.20    -- -105.00 -30.00-120.00   94
 35  \w   -173.00-142.00   0.50    0.20    -- -105.00 -61.00-120.00   62
 36  \w   -130.00 -88.00   0.50    0.20    -- -105.00 -61.00-120.00   84
 37  \w   -119.00 -24.00   0.50    0.10    --  -46.65 -77.00 -60.00  190
 38  \w   -175.00 -89.00   0.50    0.20    -- -105.00 -30.00   0.00  172
 39  \w   -151.00-126.00   0.50    0.20    -- -105.00 -83.00 -20.00   50
 40  \w    -72.00 -46.00   0.50    0.10    --  -46.65 -38.00-150.00   52
 41  \w    -29.00  22.00   0.50    0.10    --   46.65 -19.00  60.00  102
 42  \w     94.00 119.00   0.50    0.10    --   46.65 178.00 -90.00   50
 43  \w     44.00  70.00   0.50    0.10    --   46.65 178.00 -90.00   52
 44  \w     93.00 119.00   0.50    0.10    --   46.65 178.00 120.00   52
 45  \w   -112.00 -60.00   0.50    0.20    -- -105.00 125.00  90.00  104
 46  \w   -114.00 -88.00   0.50    0.20    -- -105.00-125.00 150.00   52
 47  \w   -171.00-110.00   0.50    0.20    -- -105.00 -95.00 -90.00  122
 48  \w   -165.00-139.00   0.50    0.20    -- -105.00-125.00 150.00   52
 49  \w     79.00 105.00   0.50    0.20    --  108.03 -77.00 -60.00   52
 50  \w     43.00  69.00   0.50    0.20    --  108.03 -61.00  90.00   52
 51  \w     87.00 112.00   0.50    0.20    --  108.03-125.00 -30.00   50
 52  \w     44.00  70.00   0.50    0.20    --  108.03 -77.00 -60.00   52
 53  \w     86.00 112.00   0.50    0.20    --  108.03-125.00 120.00   52
 54  \w     86.00 112.00   0.50    0.20    --  108.03-125.00  30.00   52
 55  \w     79.00 105.00   0.50    0.20    --  108.03 -77.00 150.00   52
 56  \w     83.00 112.00   0.50    0.20    --  108.03-125.00 -60.00   58
 57  \w     35.00  62.00   0.50    0.20    --  108.03 -61.00 150.00   54
 58  \w     39.00  68.00   0.50    0.20    --  108.03-125.00 -30.00   58
 59  \w   -119.00 -23.00   0.50    0.10    --  -46.65 -77.00-180.00  192
 60  \w   -119.00 -67.00   0.50    0.10    --  -46.65 -77.00  60.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1019279000
_diffrn_orient_matrix_UB_12      0.0186923000
_diffrn_orient_matrix_UB_13      -0.0802650000
_diffrn_orient_matrix_UB_21      0.1413191000
_diffrn_orient_matrix_UB_22      -0.1239438000
_diffrn_orient_matrix_UB_23      -0.0710856000
_diffrn_orient_matrix_UB_31      -0.0912061000
_diffrn_orient_matrix_UB_32      -0.1229087000
_diffrn_orient_matrix_UB_33      0.0610702000
_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  0.0350
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13882
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.598
_diffrn_reflns_theta_max         66.598
_diffrn_reflns_theta_min         3.540
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.614
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (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    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             364
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3281
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0877P)^2^+0.2023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1537
_refine_ls_wR_factor_ref         0.1643
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2572
_reflns_number_total             3281
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08263c2.cif
_cod_data_source_block           ly
_cod_depositor_comments
'Adding full bibliography for 1576597--1576598.cif.'
_cod_database_code               1576598
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHON
_cell_oxdiff_angle_alpha         84.919(2)
_cell_oxdiff_angle_beta          71.480(3)
_cell_oxdiff_angle_gamma         75.360(2)
_cell_oxdiff_length_a            8.5050(3)
_cell_oxdiff_length_b            9.0705(2)
_cell_oxdiff_length_c            13.1678(4)
_cell_oxdiff_measurement_reflns_used 7117
_cell_oxdiff_volume              931.90(5)
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.872
_diffrn_oxdiff_digest_hkl
;
016097d18a11a7f7048bb13a4ea394d9c3ec57
;
_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. Rigid bond restraints
 C19, N1
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0004
 C20, N1
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0004
 C22, C23
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0004
3.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C22(H22A,H22B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C17(H17), C14(H14), C5(H5), C3(H3), C15(H15), C4(H4), C16(H16),
 C8(H8), C11(H11), C9(H9), C10(H10)
3.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              96787
_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 1.949
_oxdiff_exptl_absorpt_empirical_full_min 0.666