Photochemical α-selective radical ring-opening reactions of 1,3-disubstituted acyl bicyclobutanes with alkyl halides: modular access to functionalized cyclobutenes.
Xiao, Yuanjiu; Xu, Tong-Tong; Zhou, Jin-Lan; Wu, Feng; Tang, Lei; Liu, Ruo-Yi; Wu, Wen-Biao; Feng, Jian-Jun; Chemical science 14 (2023) 13060–13066; doi:10.1039/d3sc04457b

data_1570204
_publ_section_title
;
 Photochemical &#x3b1;-selective radical ring-opening reactions of
 1,3-disubstituted acyl bicyclobutanes with alkyl halides: modular access
 to functionalized cyclobutenes.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              13060
_journal_page_last               13066
_journal_paper_doi               10.1039/d3sc04457b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C14 H13 N O2'
_chemical_formula_sum            'C14 H13 N O2'
_chemical_formula_weight         227.25
_chemical_name_systematic
methyl-1-(cyanomethyl)-3-phenylcyclobut-2-ene-1-carboxylate
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-08-08 deposited with the CCDC.	2023-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.998(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.84837(19)
_cell_length_b                   8.49086(12)
_cell_length_c                   14.3960(3)
_cell_measurement_reflns_used    5358
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      71.5750
_cell_measurement_theta_min      4.3890
_cell_volume                     1229.50(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -17.00  43.00   1.00    2.00    --   34.73 -57.00  90.00   60
  2  \w     31.00  73.00   1.00    2.00    --   34.73-125.00   0.00   42
  3  \w     36.00  85.00   1.00    8.00    --  105.25 -94.00 -30.00   49
  4  \w     88.00 174.00   1.00    8.00    --  105.25  45.00  90.00   86
  5  \w    116.00 162.00   1.00    8.00    --  105.25  77.00 120.00   46
  6  \w    107.00 140.00   1.00    8.00    --  105.25  96.00  19.00   33
  7  \w     83.00 111.00   1.00    8.00    --  105.25  77.00 120.00   28
  8  \w     44.00 102.00   1.00    2.00    --   34.73  77.00  60.00   58
  9  \w    106.00 161.00   1.00    8.00    --  105.25 111.00-180.00   55
 10  \w    -31.00  14.00   1.00    2.00    --   34.73 -77.00 -30.00   45
 11  \w     65.00  93.00   1.00    2.00    --   34.73  57.00 -90.00   28
 12  \w     20.00  56.00   1.00    2.00    --   34.73  57.00-150.00   36
 13  \w    -37.00  63.00   1.00    2.00    --   34.73 -19.00 150.00  100
 14  \w      3.00  73.00   1.00    2.00    --   34.73 -99.00  30.00   70
 15  \w     49.00  88.00   1.00    2.00    --   34.73-125.00-180.00   39
 16  \w     17.00  55.00   1.00    2.00    --   34.73 -99.00 -90.00   38
 17  \w     89.00 114.00   1.00    8.00    --  105.25 -45.00-120.00   25
 18  \w    113.00 152.00   1.00    8.00    --  105.25 111.00  30.00   39
 19  \w     45.00 127.00   1.00    8.00    --  105.25 -30.00  60.00   82
 20  \w     36.00 108.00   1.00    8.00    --  105.25-111.00-120.00   72
 21  \w     45.00  77.00   1.00    8.00    --  105.25 -45.00-120.00   32
 22  \w    112.00 138.00   1.00    8.00    --  105.25 111.00 -60.00   26
 23  \w     43.00 108.00   1.00    8.00    --  105.25 -94.00  30.00   65
 24  \w     76.00 121.00   1.00    8.00    --  105.25 -61.00   0.00   45
 25  \w     61.00 102.00   1.00    8.00    --  105.25 -94.00 120.00   41
 26  \w     47.00 108.00   1.00    8.00    --  105.25 -94.00 -90.00   61
 27  \w    100.00 143.00   1.00    8.00    --  105.25 111.00 150.00   43
 28  \w     44.00  70.00   1.00    8.00    --  105.25 -94.00-180.00   26
 29  \w     84.00 139.00   1.00    8.00    --  105.25  77.00-150.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1044367000
_diffrn_orient_matrix_UB_12      -0.0874469000
_diffrn_orient_matrix_UB_13      -0.0884212000
_diffrn_orient_matrix_UB_21      0.0291276000
_diffrn_orient_matrix_UB_22      -0.1531693000
_diffrn_orient_matrix_UB_23      0.0619404000
_diffrn_orient_matrix_UB_31      -0.1081371000
_diffrn_orient_matrix_UB_32      0.0431322000
_diffrn_orient_matrix_UB_33      0.0407444000
_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  0.0131
_diffrn_reflns_av_unetI/netI     0.0112
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            7732
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         4.403
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.666
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63965
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.228
_exptl_crystal_description       needle
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.299
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2160
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      3.501
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0796P)^2^+0.3909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1412
_refine_ls_wR_factor_ref         0.1439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2012
_reflns_number_total             2160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04457b2.cif
_cod_data_source_block           exp_3129
_cod_depositor_comments          'Adding full bibliography for 1570204.cif.'
_cod_database_code               1570204
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C100 H100 N2 O2'
_shelx_estimated_absorpt_t_max   0.936
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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. Restrained distances
 C7-C8
 2.9 with sigma of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C11(H11a,H11b)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C10(H10)
3.c Idealised Me refined as rotating group:
 C14(H14a,H14b,H14c)
;
_shelx_res_checksum              12295
_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 1.508
_oxdiff_exptl_absorpt_empirical_full_min 0.530