Catalyst-controlled regio- and chemodivergent C–H functionalization of imidazopyridines with TIPS-protected terminal alkynes
Zhu, Tiantian; Zhang, Qiang; Li, Xianling; Liang, Taoyuan; Zhao, Shuangliang; Zhang, Zhuan; Chemical Communications  (2026) –; doi:10.1039/D6CC01180B

data_7135721
_publ_section_title
;
 Catalyst-controlled regio- and chemodivergent C-H functionalization of
 imidazopyridines with TIPS-protected terminal alkynes.
;
_journal_issue                   34
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8752
_journal_page_last               8755
_journal_paper_doi               10.1039/d6cc01180b
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C35 H53 F N2 Si2'
_chemical_formula_sum            'C35 H53 F N2 Si2'
_chemical_formula_weight         576.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-02-04 deposited with the CCDC.	2026-04-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.780(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.0162(10)
_cell_length_b                   14.2172(11)
_cell_length_c                   14.0720(11)
_cell_measurement_reflns_used    4387
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.4940
_cell_measurement_theta_min      3.0640
_cell_volume                     3600.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.99a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0606
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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      9.00  43.00   1.00    3.00    --   35.25  19.00   0.00   34
  2  \w    -30.00  47.00   1.00    3.00    --   35.25 -57.00 120.00   77
  3  \w    -32.00  34.00   1.00    3.00    --   35.25 -37.00   0.00   66
  4  \w     25.00  72.00   1.00    3.00    --   35.25 -99.00-120.00   47
  5  \w     36.00  87.00   1.00    3.00    --   35.25-125.00  30.00   51
  6  \w     46.00  79.00   1.00    3.00    --   35.25-125.00-180.00   33
  7  \w     39.00  86.00   1.00    3.00    --   35.25  57.00  90.00   47
  8  \w     21.00 101.00   1.00    3.00    --   35.25  37.00   0.00   80
  9  \w    -34.00  49.00   1.00    3.00    --   35.25 -37.00-180.00   83
 10  \w     37.00  62.00   1.00    2.50    --  105.75 -94.00 -60.00   25
 11  \w     45.00  84.00   1.00    2.50    --  105.75-111.00 -60.00   39
 12  \w     44.00 127.00   1.00    2.50    --  105.75 -30.00 -90.00   83
 13  \w     76.00 108.00   1.00    2.50    --  105.75-111.00 -30.00   32
 14  \w    113.00 139.00   1.00    2.50    --  105.75 178.00-180.00   26
 15  \w    138.00 164.00   1.00    2.50    --  105.75  77.00  30.00   26
 16  \w     65.00 108.00   1.00    2.50    --  105.75-111.00  60.00   43
 17  \w    116.00 173.00   1.00    2.50    --  105.75  45.00  60.00   57
 18  \w    102.00 168.00   1.00    2.50    --  105.75  61.00  90.00   66
 19  \w    105.00 137.00   1.00    2.50    --  105.75  77.00 -30.00   32
 20  \w    110.00 168.00   1.00    2.50    --  105.75 111.00   0.00   58
 21  \w     71.00 108.00   1.00    2.50    --  105.75-111.00-120.00   37
 22  \w     44.00  83.00   1.00    2.50    --  105.75-111.00-150.00   39
 23  \w     39.00 123.00   1.00    2.50    --  105.75 -45.00   0.00   84
 24  \w    102.00 165.00   1.00    2.50    --  105.75  77.00 -60.00   63
 25  \w     60.00 107.00   1.00    2.50    --  105.75-111.00 150.00   47
 26  \w    104.00 157.00   1.00    2.50    --  105.75 111.00 -30.00   53
 27  \w     54.00 119.00   1.00    2.50    --  105.75 -61.00 -90.00   65
 28  \w    104.00 130.00   1.00    2.50    --  105.75  77.00  30.00   26
 29  \w    114.00 161.00   1.00    2.50    --  105.75 111.00 -90.00   47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0309928000
_diffrn_orient_matrix_UB_12      0.0684981000
_diffrn_orient_matrix_UB_13      0.0767975000
_diffrn_orient_matrix_UB_21      0.0629422000
_diffrn_orient_matrix_UB_22      -0.0700040000
_diffrn_orient_matrix_UB_23      0.0266244000
_diffrn_orient_matrix_UB_31      0.0489946000
_diffrn_orient_matrix_UB_32      0.0463716000
_diffrn_orient_matrix_UB_33      -0.0736101000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0613
_diffrn_reflns_av_unetI/netI     0.0543
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23967
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.954
_diffrn_reflns_theta_min         2.455
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.107
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11554
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.99a (Rigaku Oxford Diffraction, 2023)
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    1.064
_exptl_crystal_description       block
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.042
_refine_ls_extinction_coef       0.0016(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     447
_refine_ls_number_reflns         6843
_refine_ls_number_restraints     433
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0651
_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^)+(0.0851P)^2^+0.8279P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1702
_refine_ls_wR_factor_ref         0.1944
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4811
_reflns_number_total             6843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc01180b2.cif
_cod_data_source_block           exp_15173_auto
_cod_depositor_comments
'Adding full bibliography for 7135720--7135721.cif.'
_cod_database_code               7135721
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.869
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C7-N2 \\sim C0-N0
 with sigma of 0.02
 C7-C6 \\sim C0-C6
 with sigma of 0.02
 N2-C5 \\sim N0-C36
 with sigma of 0.02
 N2-C4 \\sim N0-C38
 with sigma of 0.02
 N1-C5 \\sim N3-C36
 with sigma of 0.02
 N1-C6 \\sim N3-C6
 with sigma of 0.02
 C5-C1 \\sim C36-C37
 with sigma of 0.02
 C1-C2 \\sim C37-C40
 with sigma of 0.02
 C4-C3 \\sim C38-C39
 with sigma of 0.02
 C3-C2 \\sim C39-C40
 with sigma of 0.02
 C7-N1 \\sim C0-N3
 with sigma of 0.04
 C7-C5 \\sim C0-C36
 with sigma of 0.04
 C7-C8 \\sim C0-C8
 with sigma of 0.04
 C7-C4 \\sim C0-C38
 with sigma of 0.04
 N2-N1 \\sim N0-N3
 with sigma of 0.04
 N2-C6 \\sim N0-C6
 with sigma of 0.04
 N2-C1 \\sim N0-C37
 with sigma of 0.04
 N2-C3 \\sim N0-C39
 with sigma of 0.04
 N1-C8 \\sim N3-C8
 with sigma of 0.04
 N1-C1 \\sim N3-C37
 with sigma of 0.04
 C5-C6 \\sim C36-C6
 with sigma of 0.04
 C5-C4 \\sim C36-C38
 with sigma of 0.04
 C5-C2 \\sim C36-C40
 with sigma of 0.04
 C1-C3 \\sim C37-C39
 with sigma of 0.04
 C4-C2 \\sim C38-C40
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C7 \\sim N2 \\sim N1 \\sim C5 \\sim C6 \\sim C1 \\sim C4 \\sim C3 \\sim C2
\\sim C0 \\sim N0 \\sim N3 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C7, N2, N1, C5, C6, C1, C4, C3, C2, C0, N0, N3, C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C0)=Sof(H0)=Sof(N0)=Sof(N3)=Sof(C36)=Sof(C37)=Sof(H2A)=Sof(C38)=Sof(H3)=
 Sof(C39)=Sof(H4)=Sof(C40)=Sof(H5)=1-FVAR(1)
 Sof(C7)=Sof(H7)=Sof(N2)=Sof(N1)=Sof(C5)=Sof(C1)=Sof(H1)=Sof(C4)=Sof(H4A)=
 Sof(C3)=Sof(H3A)=Sof(C2)=Sof(H2)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C27(H27), C16(H16), C22(H22), C19(H19), C30(H30), C33(H33)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C25(H25), C14(H14), C15(H15), C10(H10), C1(H1), C26(H26), C12(H12),
 C4(H4A), C3(H3A), C2(H2), C0(H0), C37(H2A), C38(H3), C39(H4), C40(H5)
6.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C29(H29A,H29B,H29C), C23(H23A,H23B,H23C), C34(H34A,H34B,
 H34C), C18(H18A,H18B,H18C), C28(H28A,H28B,H28C), C17(H17A,H17B,H17C), C21(H21A,
 H21B,H21C), C20(H20A,H20B,H20C), C32(H32A,H32B,H32C), C31(H31A,H31B,H31C),
 C35(H35A,H35B,H35C)
;
_shelx_res_checksum              90216
_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 4.302
_oxdiff_exptl_absorpt_empirical_full_min 0.414