Synthesis of Diverse Substituted Pyrimidines through Cu Catalyst-Controlled Ts Group's Elimination and Reinsertion Pathway from 2H-Azirines with TosMICs
Cheng, Wen; Li, Mengfan; tang, hao; wang, yuxi; yu, qiurou; Bao, Xiaoli; Zhao, Yun-Hui; Yi, Weiyin; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D5OB01962A

data_7160939
_publ_section_title
;
 Synthesis of diverse substituted pyrimidines through Cu
 catalyst-controlled Ts group elimination and reinsertion pathway from
 2<i>H</i>-azirines with TosMICs.
;
_journal_issue                   10
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2046
_journal_page_last               2060
_journal_paper_doi               10.1039/d5ob01962a
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C16 H12 N2'
_chemical_formula_sum            'C16 H12 N2'
_chemical_formula_weight         232.28
_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             2024-03-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-06-28 deposited with the CCDC.	2026-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.506(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7603(4)
_cell_length_b                   6.9704(2)
_cell_length_c                   14.8503(6)
_cell_measurement_reflns_used    6466
_cell_measurement_temperature    293
_cell_measurement_theta_max      73.6300
_cell_measurement_theta_min      4.7360
_cell_volume                     1216.92(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_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   -125.00 -95.00   0.50    0.05    --  -39.95-178.00  60.00   60
  2  \w    -54.00  29.00   0.50    0.05    --  -39.95  57.00   0.00  166
  3  \w    -42.00  39.00   0.50    0.05    --  -39.95  37.00  90.00  162
  4  \w   -107.00 -80.00   0.50    0.05    --  -39.95 -57.00 -60.00   54
  5  \w    -69.00 -43.00   0.50    0.05    --  -39.95-178.00  60.00   52
  6  \w    -50.00 -13.00   0.50    0.05    --  -39.95 -57.00 -60.00   74
  7  \w     70.00 107.00   0.50    0.05    --   39.95 178.00-120.00   74
  8  \w     63.00 114.00   0.50    0.05    --   39.95 178.00 -30.00  102
  9  \w    -51.00 -17.00   0.50    0.18    --  -94.50  45.00 120.00   68
 10  \w    -51.00 -16.00   0.50    0.18    --  -94.50  45.00-150.00   70
 11  \w    -71.00 -42.00   0.50    0.18    --  -94.50  61.00   0.00   58
 12  \w    -46.00 -15.00   0.50    0.18    --  -94.50  45.00 150.00   62
 13  \w    -57.00 -17.00   0.50    0.18    --  -94.50 125.00-120.00   80
 14  \w   -116.00 -82.00   0.50    0.18    --  -94.50-125.00   0.00   68
 15  \w    -71.00 -41.00   0.50    0.18    --  -94.50  61.00  30.00   60
 16  \w   -175.00-127.00   0.50    0.18    --  -94.50 -30.00   0.00   96
 17  \w   -107.00 -81.00   0.50    0.18    --  -94.50 -30.00   0.00   52
 18  \w    -86.00 -47.00   0.50    0.18    --  -94.50 125.00  30.00   78
 19  \w    -51.00 -20.00   0.50    0.18    --  -94.50  45.00 -90.00   62
 20  \w    -51.00 -19.00   0.50    0.18    --  -94.50  45.00 -60.00   64
 21  \w    -51.00 -17.00   0.50    0.18    --  -94.50  45.00-120.00   68
 22  \w     37.00 103.00   0.50    0.18    --  108.87-125.00  60.00  132
 23  \w     71.00 106.00   0.50    0.18    --  108.87 -77.00  30.00   70
 24  \w     77.00 102.00   0.50    0.18    --  108.87-125.00 -90.00   50
 25  \w     48.00  74.00   0.50    0.18    --  108.87-125.00 -90.00   52
 26  \w     48.00 101.00   0.50    0.18    --  108.87 -94.00 -60.00  106
 27  \w     74.00 106.00   0.50    0.18    --  108.87 -77.00 150.00   64
 28  \w    138.00 178.00   0.50    0.18    --  108.87  61.00 -30.00   80
 29  \w     92.00 132.00   0.50    0.18    --  108.87  61.00 -30.00   80
 30  \w     74.00 101.00   0.50    0.18    --  108.87 -94.00 150.00   54
 31  \w     39.00  65.00   0.50    0.18    --  108.87 -61.00  90.00   52
 32  \w     34.00  68.00   0.50    0.18    --  108.87 -94.00 150.00   68
 33  \w     75.00 111.00   0.50    0.18    --  108.87-125.00 -60.00   72
 34  \w    134.00 175.00   0.50    0.18    --  108.87  61.00  90.00   82
 35  \w     80.00 128.00   0.50    0.18    --  108.87  61.00  90.00   96
 36  \w    129.00 157.00   0.50    0.18    --  108.87  45.00-180.00   56
 37  \w     72.00 178.00   0.50    0.18    --  108.87  30.00  60.00  212
 38  \w     86.00 119.00   0.50    0.18    --  108.87  45.00-180.00   66
 39  \w     71.00 104.00   0.50    0.18    --  108.87 -94.00 120.00   66
 40  \w     29.00  72.00   0.50    0.18    --  108.87 -94.00 -90.00   86
 41  \w     82.00 116.00   0.50    0.18    --  108.87-131.00  90.28   68
 42  \w     86.00 111.00   0.50    0.18    --  108.87-125.00 -30.00   50
 43  \w     48.00  78.00   0.50    0.18    --  108.87-131.00  90.28   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0992466000
_diffrn_orient_matrix_UB_12      -0.0950678000
_diffrn_orient_matrix_UB_13      -0.0489388000
_diffrn_orient_matrix_UB_21      -0.0702214000
_diffrn_orient_matrix_UB_22      0.0042552000
_diffrn_orient_matrix_UB_23      -0.0889627000
_diffrn_orient_matrix_UB_31      0.0488389000
_diffrn_orient_matrix_UB_32      0.1995477000
_diffrn_orient_matrix_UB_33      -0.0213757000
_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  0.0537
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10672
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.861
_diffrn_reflns_theta_min         4.736
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.589
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.49a (Rigaku Oxford Diffraction, 2019)
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    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.200
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.0077(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2413
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0435
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0799P)^2^+0.0749P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1239
_refine_ls_wR_factor_ref         0.1283
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2159
_reflns_number_total             2413
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01962a2.cif
_cod_data_source_block           0314-1
_cod_depositor_comments
'Adding full bibliography for 7160938--7160939.cif.'
_cod_database_code               7160939
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.843
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16)
;
_shelx_res_checksum              99440
_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 2.332
_oxdiff_exptl_absorpt_empirical_full_min 0.464