Synthesis of polysubstituted cyclobutanes through a photoredox strain-release/[3,3]-rearrangement cascade
Zhang, Fangqing; Xu, Chun; Zhang, Zichun; Yang, Zhuang; Peng, Tao; Shao, Wen; Feng, Xiaoming; Liu, Yangbin; Chemical Science 16 (2025) 11508–11518; doi:10.1039/D5SC01431J

data_1574745
_publ_section_title
;
 Synthesis of polysubstituted cyclobutanes through a photoredox
 strain-release/[3,3]-rearrangement cascade
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              11508
_journal_page_last               11518
_journal_paper_doi               10.1039/D5SC01431J
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C20 H34 N2 O4'
_chemical_formula_sum            'C20 H34 N2 O4'
_chemical_formula_weight         366.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-08-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-19 deposited with the CCDC.	2025-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.8770(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.4619(3)
_cell_length_b                   6.33880(10)
_cell_length_c                   26.1419(3)
_cell_measurement_reflns_used    13927
_cell_measurement_temperature    300.69(10)
_cell_measurement_theta_max      76.8910
_cell_measurement_theta_min      3.3950
_cell_volume                     4291.08(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.69(10)
_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 0.968
_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     33.00 108.00   0.50    0.05    --  105.65 -77.00 150.00  150
  2  \w     79.00 104.00   0.50    0.05    --  105.65 -94.00   0.00   50
  3  \w     80.00 105.00   0.50    0.05    --  105.65 -94.00 -30.00   50
  4  \w     47.00  72.00   0.50    0.05    --  105.65 -61.00  30.00   50
  5  \w     33.00  61.00   0.50    0.05    --  105.65 -94.00 -30.00   56
  6  \w     34.00  64.00   0.50    0.05    --  105.65 -61.00 -90.00   60
  7  \w     43.00  91.00   0.50    0.05    --  105.65 -72.00-106.00   96
  8  \w    -25.00  54.00   0.50    0.05    --   46.54 -72.00-106.00  158
  9  \w    123.00 165.00   0.50    0.05    --  105.65  30.00 -30.00   84
 10  \w    113.00 167.00   0.50    0.05    --  105.65  45.00 -60.00  108
 11  \w    149.00 176.00   0.50    0.05    --  105.65  72.00  23.00   54
 12  \w    141.00 166.00   0.50    0.05    --  105.65  45.00 150.00   50
 13  \w     95.00 120.00   0.50    0.05    --  105.65  45.00 150.00   50
 14  \w     60.00 107.00   0.50    0.05    --   46.54  72.00  23.00   94
 15  \w    -54.00  26.00   0.50    0.05    --  -46.54  72.00  23.00  160
 16  \w    -25.00  28.00   0.50    0.05    --  -46.54  19.00 120.00  106
 17  \w    -15.00  29.00   0.50    0.05    --  -46.54  19.00  30.00   88
 18  \w    -24.00  23.00   0.50    0.05    --  -46.54  19.00   0.00   94
 19  \w    -23.00  29.00   0.50    0.05    --  -46.54  19.00-180.00  104
 20  \w    -69.00 -44.00   0.50    0.05    -- -104.00  61.00-120.00   50
 21  \w    -65.00 -39.00   0.50    0.05    -- -104.00  61.00-150.00   52
 22  \w    -89.00 -31.00   0.50    0.05    -- -104.00  72.00  23.00  116
 23  \w    -66.00 -32.00   0.50    0.05    -- -104.00  61.00  90.00   68
 24  \w    -65.00 -39.00   0.50    0.05    -- -104.00  61.00 150.00   52
 25  \w   -131.00 -90.00   0.50    0.05    -- -104.00 -15.00 150.00   82
 26  \w   -155.00 -92.00   0.50    0.05    -- -104.00 -45.00 150.00  126
 27  \w    -96.00 -71.00   0.50    0.05    --  -46.54 -72.00-106.00   50
 28  \w   -128.00-102.00   0.50    0.05    -- -104.00 -77.00-150.00   52
 29  \w   -171.00-136.00   0.50    0.05    -- -104.00 -77.00-150.00   70
 30  \w   -164.00 -96.00   0.50    0.05    -- -104.00 -72.00-106.00  136
 31  \w   -171.00-101.00   0.50    0.05    -- -104.00 -45.00 -60.00  140
 32  \w   -171.00 -91.00   0.50    0.05    -- -104.00 -30.00  90.00  160
 33  \w   -175.00 -91.00   0.50    0.05    -- -104.00 -30.00 120.00  168
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0351754000
_diffrn_orient_matrix_UB_12      0.1466638000
_diffrn_orient_matrix_UB_13      -0.0242258000
_diffrn_orient_matrix_UB_21      0.0475066000
_diffrn_orient_matrix_UB_22      -0.1292810000
_diffrn_orient_matrix_UB_23      0.0265145000
_diffrn_orient_matrix_UB_31      -0.0068273000
_diffrn_orient_matrix_UB_32      -0.1443239000
_diffrn_orient_matrix_UB_33      -0.0483305000
_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  0.0200
_diffrn_reflns_av_unetI/netI     0.0131
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            22227
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.061
_diffrn_reflns_theta_min         3.413
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.631
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76302
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
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    1.135
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.695
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         4373
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0725
_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^)+(0.1390P)^2^+2.2637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2273
_refine_ls_wR_factor_ref         0.2345
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3782
_reflns_number_total             4373
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01431j2.cif
_cod_data_source_block           zfq-6-1-20240813_auto
_cod_depositor_comments
'Adding full bibliography for 1574745--1574746.cif.'
_cod_database_code               1574745
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C H O N'
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.884
_olex2_refinement_description
;
1. Rigid bond restraints
 C00A, C00N
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
2.a Ternary CH refined with riding coordinates:
 C00H(H00L)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00A,H00B), C00B(H00D,H00E), C00C(H00F,H00G), C00F(H00H,H00I), C00G(H00J,
 H00K), C00I(H00M,H00N), C00J(H00O,H00P)
2.c Aromatic/amide H refined with riding coordinates:
 C00A(H00C)
2.d X=CH2 refined with riding coordinates:
 C00N(H00W,H00X)
2.e Idealised Me refined as rotating group:
 C00L(H00Q,H00R,H00S), C00M(H00T,H00U,H00V), C00O(H00Y,H,HA), C00P(H00Z,HB,HC),
  C00Q(H00,HD,HE)
2.f Idealised tetrahedral OH refined as rotating group:
 O001(H001)
;
_shelx_res_checksum              79032
_shelx_hkl_checksum              82122
_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 1.263
_oxdiff_exptl_absorpt_empirical_full_min 0.848