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_1576597
_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         'C19 H18 N2 O3'
_chemical_formula_sum            'C19 H18 N2 O3'
_chemical_formula_weight         322.35
_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     direct
_audit_creation_date             2022-03-29
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-03-10 deposited with the CCDC.	2025-12-19 downloaded from the CCDC.
;
_cell_angle_alpha                90.483(7)
_cell_angle_beta                 97.956(7)
_cell_angle_gamma                100.119(6)
_cell_formula_units_Z            4
_cell_length_a                   9.5496(7)
_cell_length_b                   10.1080(8)
_cell_length_c                   17.3620(16)
_cell_measurement_reflns_used    3870
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      26.9130
_cell_measurement_theta_min      2.0750
_cell_volume                     1633.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_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    -14.00  85.00   1.00    6.00    --   11.90  57.00  60.00   99
  2  \w     35.00  61.00   1.00    6.00    --   11.90 178.00-120.00   26
  3  \w    -14.00  78.00   1.00    6.00    --   11.90  77.00-180.00   92
  4  \w    -55.00  38.00   1.00    6.00    --   11.90 -57.00 -90.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0205972000
_diffrn_orient_matrix_UB_12      -0.0155691000
_diffrn_orient_matrix_UB_13      0.0370504000
_diffrn_orient_matrix_UB_21      0.0537493000
_diffrn_orient_matrix_UB_22      0.0534923000
_diffrn_orient_matrix_UB_23      0.0173014000
_diffrn_orient_matrix_UB_31      -0.0499669000
_diffrn_orient_matrix_UB_32      0.0445295000
_diffrn_orient_matrix_UB_33      -0.0056093000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1252
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            5743
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.039
_diffrn_reflns_theta_max         25.039
_diffrn_reflns_theta_min         2.048
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59133
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.603
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         5743
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.1432
_refine_ls_R_factor_gt           0.1126
_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^)+(0.1342P)^2^+2.2491P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2851
_refine_ls_wR_factor_ref         0.3080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3953
_reflns_number_total             5743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08263c2.cif
_cod_data_source_block           409
_cod_depositor_comments
'Adding full bibliography for 1576597--1576598.cif.'
_cod_database_code               1576597
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.679(7)
 0.321(7)
2. 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
3.a Ternary CH refined with riding coordinates:
 C35(H35), C9(H9), C34(H34), C10(H10)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C26(H26A,H26B), C37(H37A,H37B), C18(H18A,H18B)
3.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C6(H6), C17(H17), C2(H2), C25(H25), C24(H24), C23(H23), C14(H14),
 C32(H32), C31(H31), C22(H22), C30(H30), C29(H29), C16(H16), C15(H15), C4(H4),
 C5(H5), C3(H3)
3.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              88749
_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 1.566
_oxdiff_exptl_absorpt_empirical_full_min 0.644