Photosensitized diradical rearrangement of alkenyl oxime ethers towards amino-featured oxiranes: reaction, mechanism, and structural prediction.
Liu, Tu-Ming; Zhu, Lin-Yuan; Qi, Min-Hao; Li, Si-Jia; Wang, Xiao-Jian; Xu, Jia-Rui; Han, Bing; Chemical science 16 (2025) 14811–14821; doi:10.1039/d5sc03379a

data_1575160
_publ_section_title
;
 Photosensitized diradical rearrangement of alkenyl oxime ethers towards
 amino-featured oxiranes: reaction, mechanism, and structural prediction.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              14811
_journal_page_last               14821
_journal_paper_doi               10.1039/d5sc03379a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C28 H22 Br N O'
_chemical_formula_sum            'C28 H22 Br N O'
_chemical_formula_weight         468.37
_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             2025-03-13
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-03-31 deposited with the CCDC.	2025-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                69.915(3)
_cell_angle_beta                 81.048(2)
_cell_angle_gamma                86.989(2)
_cell_formula_units_Z            2
_cell_length_a                   5.8212(2)
_cell_length_b                   14.1940(4)
_cell_length_c                   14.7214(5)
_cell_measurement_reflns_used    6241
_cell_measurement_temperature    149.97(10)
_cell_measurement_theta_max      74.0300
_cell_measurement_theta_min      3.2670
_cell_volume                     1128.48(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.97(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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     81.00 158.00   0.50    0.97    --  108.93 125.00-120.00  154
  2  \w      0.00  33.00   0.50    0.24    --   44.63 -37.00 -60.00   66
  3  \w    -30.00  -5.00   0.50    0.24    --   44.63 -37.00 -60.00   50
  4  \w    -25.00   1.00   0.50    0.24    --   44.63 -64.00  66.00   52
  5  \w     16.00  66.00   0.50    0.24    --   44.63 -64.00  66.00  100
  6  \w    -27.00  23.00   0.50    0.24    --   44.63 -19.00  60.00  100
  7  \w     44.00 112.00   0.50    0.24    --   44.63  64.00-157.00  136
  8  \w    135.00 164.00   0.50    0.97    --  108.93  45.00-120.00   58
  9  \w     91.00 168.00   0.50    0.97    --  108.93  64.00-157.00  154
 10  \w     96.00 121.00   0.50    0.97    --  108.93  45.00-120.00   50
 11  \w     88.00 130.00   0.50    0.97    --  108.93  15.00-180.00   84
 12  \w    140.00 168.00   0.50    0.97    --  108.93  15.00-180.00   56
 13  \w     94.00 163.00   0.50    0.97    --  108.93  45.00 -30.00  138
 14  \w    122.00 151.00   0.50    0.97    --  108.93  61.00 120.00   58
 15  \w     35.00  72.00   0.50    0.97    --  108.93 -64.00  66.00   74
 16  \w     77.00 102.00   0.50    0.97    --  108.93 -94.00 150.00   50
 17  \w     53.00  79.00   0.50    0.97    --  108.93 -94.00  90.00   52
 18  \w     39.00 106.00   0.50    0.97    --  108.93 -94.00  30.00  134
 19  \w     67.00  92.00   0.50    0.97    --  108.93 -94.00-120.00   50
 20  \w     56.00 111.00   0.50    0.97    --  108.93-125.00-180.00  110
 21  \w     -3.00  25.00   0.50    0.24    --  -44.63  64.00-157.00   56
 22  \w    -45.00 -18.00   0.50    0.24    --  -44.63  64.00-157.00   54
 23  \w   -123.00 -60.00   0.50    0.97    -- -100.00 141.00-102.01  126
 24  \w    -81.00 -52.00   0.50    0.97    -- -100.00 125.00 -60.00   58
 25  \w    -59.00 -31.00   0.50    0.97    -- -100.00 125.00 -30.00   56
 26  \w   -111.00 -73.00   0.50    0.97    -- -100.00 125.00 -30.00   76
 27  \w   -112.00 -74.00   0.50    0.97    -- -100.00 125.00  90.00   76
 28  \w    -12.00  33.00   0.50    0.24    --  -44.63  19.00   0.00   90
 29  \w   -110.00 -29.00   0.50    0.97    -- -100.00 125.00-150.00  162
 30  \w    -79.00 -37.00   0.50    0.97    -- -100.00  64.00-157.00   84
 31  \w    -54.00 -26.00   0.50    0.97    -- -100.00  45.00-150.00   56
 32  \w    -62.00 -30.00   0.50    0.97    -- -100.00  61.00-120.00   64
 33  \w    -71.00 -27.00   0.50    0.97    -- -100.00  61.00 -30.00   88
 34  \w    -54.00 -28.00   0.50    0.97    -- -100.00  45.00  30.00   52
 35  \w    -51.00 -25.00   0.50    0.97    -- -100.00  45.00  60.00   52
 36  \w   -172.00 -78.00   0.50    0.97    -- -100.00 -64.00  66.00  188
 37  \w   -157.00 -83.00   0.50    0.97    -- -100.00-125.00 150.00  148
 38  \w   -115.00 -56.00   0.50    0.24    --  -44.63-179.00 120.00  118
 39  \w   -105.00 -31.00   0.50    0.24    --  -44.63 -64.00  66.00  148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1098309000
_diffrn_orient_matrix_UB_12      -0.0991017000
_diffrn_orient_matrix_UB_13      0.0584572000
_diffrn_orient_matrix_UB_21      0.2399333000
_diffrn_orient_matrix_UB_22      0.0364240000
_diffrn_orient_matrix_UB_23      -0.0597756000
_diffrn_orient_matrix_UB_31      0.0463056000
_diffrn_orient_matrix_UB_32      0.0469825000
_diffrn_orient_matrix_UB_33      0.0754849000
_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  0.0341
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11567
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         3.231
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.625
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (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    1.378
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.999
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         3928
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0601P)^2^+1.4475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1222
_refine_ls_wR_factor_ref         0.1255
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3418
_reflns_number_total             3928
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03379a2.cif
_cod_data_source_block           liutuming-hb_0313_auto
_cod_depositor_comments          'Adding full bibliography for 1575160.cif.'
_cod_database_code               1575160
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C8(H8), C9(H9), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C19(H19), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28)
;
_shelx_res_checksum              59857
_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 1.462
_oxdiff_exptl_absorpt_empirical_full_min 0.639