Reactivity of p-Toluenesulfonylmethyl Isocyanide: Iron-Involved C-H Tosylmethylation of Imidazopyridines in Nontoxic Media.
Lu, Shuai; Zhu, Xinju; Li, Ke; Guo, Yu-Jing; Wang, Meng-Dan; Zhao, Xue-Mei; Hao, Xin-Qi; Song, Mao-Ping; The Journal of organic chemistry 81 (2016) 8370–8377; doi:10.1021/acs.joc.6b01552

data_4037115
_publ_section_title
;
 Reactivity of p-Toluenesulfonylmethyl Isocyanide: Iron-Involved C-H
 Tosylmethylation of Imidazopyridines in Nontoxic Media.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8370
_journal_page_last               8377
_journal_paper_doi               10.1021/acs.joc.6b01552
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C16 H15 N O2 S'
_chemical_formula_sum            'C16 H15 N O2 S'
_chemical_formula_weight         285.35
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                78.356(4)
_cell_angle_beta                 88.040(5)
_cell_angle_gamma                83.470(4)
_cell_formula_units_Z            8
_cell_length_a                   11.0146(6)
_cell_length_b                   14.8262(6)
_cell_length_c                   18.3192(10)
_cell_measurement_reflns_used    6650
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6810
_cell_measurement_theta_min      4.2950
_cell_volume                     2910.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega -102.00  -15.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000  -30.0000 87

  2 omega  -51.00  -12.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000  120.0000 39

  3 omega   20.00   73.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000   90.0000 53

  4 omega   29.00   55.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -30.0000 26

  5 omega  -32.00   -4.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  150.0000 28

  6 omega   -4.00   72.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  150.0000 76

  7 omega   23.00   74.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000    0.0000 51

  8 omega   25.00   51.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  -60.0000 26

  9 omega  -32.00   13.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000 -150.0000 45

 10 omega   61.00   98.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -30.0000 37

 11 omega   20.00   64.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000 -150.0000 44

 12 omega   15.00   85.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000  150.0000 70

 13 omega   16.00   42.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  150.0000 26

 14 omega   76.00  110.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -90.0000 34

 15 omega  -33.00   58.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000 -150.0000 91

 16 omega  -19.00    7.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000 -180.0000 26

 17 omega   36.00   91.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   30.0000 55

 18 omega   82.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 27

 19 omega   41.00  115.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 74

 20 omega   38.00   73.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 35

 21 omega   65.00  115.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -30.0000 50

 22 omega   47.00   74.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 27

 23 omega   38.00   98.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 60

 24 omega   54.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 55

 25 omega   37.00   87.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 50

 26 omega   39.00  127.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -120.0000 88

 27 omega   40.00   98.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 58

 28 omega   52.00   77.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 25

 29 omega   38.00   90.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 52

 30 omega   39.00   86.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 47

 31 omega  144.00  177.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -60.0000 33

 32 omega   76.00  102.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 26

 33 omega  112.00  147.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   30.0000 35

 34 omega   40.00  109.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   30.0000 69

 35 omega   63.00  169.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   60.0000 106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1164454000
_diffrn_orient_matrix_UB_12      -0.0230296000
_diffrn_orient_matrix_UB_13      -0.0333882000
_diffrn_orient_matrix_UB_21      0.0763781000
_diffrn_orient_matrix_UB_22      -0.0295057000
_diffrn_orient_matrix_UB_23      -0.0649628000
_diffrn_orient_matrix_UB_31      0.0206888000
_diffrn_orient_matrix_UB_32      -0.0999504000
_diffrn_orient_matrix_UB_33      0.0451482000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            21473
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         3.527
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.979
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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    1.302
_exptl_crystal_description       needle
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         10370
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0698
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0758P)^2^+0.3080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1285
_refine_ls_wR_factor_ref         0.1442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7601
_reflns_number_total             10370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01552_si_003.cif
_cod_data_source_block           20160691
_cod_original_cell_volume        2910.9(3)
_cod_database_code               4037115
_chemical_oxdiff_formula         C1H1O1N4S1
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9B(H9BA,H9BB), C9A(H9AA,H9AB), C9C(H9CA,H9CB)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C11(H11), C12(H12), C14(H14),
 C15(H15), C1B(H1BA), C2B(H2B), C3B(H3B), C4B(H4B), C8B(H8B), C11B(H11B),
 C12B(H12B), C14B(H14B), C15B(H15B), C1A(H1AA), C2A(H2A), C3A(H3A), C4A(H4A),
 C8A(H8A), C11A(H11A), C12A(H12A), C14A(H14A), C15A(H15A), C1C(H1CA), C2C(H2C),
 C3C(H3C), C4C(H4C), C8C(H8C), C11C(H11C), C12C(H12C), C14C(H14C), C15C(H15C)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C16B(H16D,H16E,H16F), C16A(H16J,H16K,H16L), C16C(H16G,
 H16H,H16I)
;
_shelx_res_checksum              53739
_shelx_hkl_checksum              1558
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'