Addition of N-heterocyclic carbenes to imines: phenoxide assisted deprotonation of an imidazolium moiety and generation of breslow intermediates derived from imines.
Simonovic, Stevan; Frison, Jean-Cédric; Koyuncu, Hasan; Whitwood, Adrian C.; Douthwaite, Richard E.; Organic letters 11 (2009) 245–247; doi:10.1021/ol802572n

data_1503750
_publ_section_title
;
 Addition of N-heterocyclic carbenes to imines: phenoxide assisted
 deprotonation of an imidazolium moiety and generation of breslow
 intermediates derived from imines.
;
_journal_issue                   1
_journal_name_full               'Organic letters'
_journal_page_first              245
_journal_page_last               247
_journal_paper_doi               10.1021/ol802572n
_journal_volume                  11
_journal_year                    2009
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H28 N4 O3'
_chemical_formula_sum            'C25 H28 N4 O3'
_chemical_formula_weight         432.51
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
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_atom_sites_solution_hydrogens   geom
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_audit_creation_date
;
'Thu Jul 10 22:07:42 2008'
;
_audit_creation_method
;
ShellX-97/CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_cell_angle_alpha                90.0
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_computing_cell_refinement
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_data_collection
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CrysAlis CCD, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_data_reduction
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CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
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_diffrn_measurement_details
;
  1 omega  -65.00   -6.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937  -77.0000  300.0000    0.0000    0.0000 59

  2 omega   34.00   90.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   77.0000   30.0000    0.0000    0.0000 56

  3 omega   35.00   88.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   44.0000  158.0000    0.0000    0.0000 53

  4 omega  -36.00   11.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937   45.0000   60.0000    0.0000    0.0000 47

  5 omega  -58.00  -10.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937  -45.0000   90.0000    0.0000    0.0000 48

  6 omega   36.00   92.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -       13.7937   77.0000  210.0000    0.0000    0.0000 56

  7 omega  -82.00  -55.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -13.7937  -44.0000  187.0000    0.0000    0.0000 27

  8 omega -117.00  -59.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  -77.0000  240.0000    0.0000    0.0000 58

  9 omega -127.00  -14.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000   77.0000  150.0000    0.0000    0.0000 113

 10 omega  -65.00   -6.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000    0.0000  150.0000    0.0000    0.0000 59

 11 omega -118.00  -65.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  -45.0000   60.0000    0.0000    0.0000 53

 12 omega -122.00  -61.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000    0.0000    0.0000    0.0000    0.0000 61

 13 omega -117.00  -67.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  -44.0000   21.0000    0.0000    0.0000 50

 14 omega -166.00 -114.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  -45.0000  330.0000    0.0000    0.0000 52

 15 omega -167.00 -122.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000  -45.0000   30.0000    0.0000    0.0000 45

 16 omega  -65.00   -6.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      -93.0000    0.0000   90.0000    0.0000    0.0000 59

 17 omega   26.00   78.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000   30.0000    0.0000    0.0000 52

 18 omega   89.00  128.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  270.0000    0.0000    0.0000 39

 19 omega   72.00  114.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   44.0000  172.0000    0.0000    0.0000 42

 20 omega   77.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000   45.0000  270.0000    0.0000    0.0000 32

 21 omega   25.00   79.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -77.0000  120.0000    0.0000    0.0000 54

 22 omega   22.00   79.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -77.0000  196.0000    0.0000    0.0000 57

 23 omega   80.00  111.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ omega'___ theta'___ frames
    -      100.0000  -45.0000  150.0000    0.0000    0.0000 31

;
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_diffrn_orient_matrix_UB_21      0.0267108018
_diffrn_orient_matrix_UB_22      0.1448265027
_diffrn_orient_matrix_UB_23      -0.0636057066
_diffrn_orient_matrix_UB_31      -0.0082829786
_diffrn_orient_matrix_UB_32      -0.0967763658
_diffrn_orient_matrix_UB_33      -0.0974919402
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'Enhance (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0236
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_diffrn_reflns_limit_h_max       11
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_diffrn_reflns_limit_l_max       15
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_diffrn_reflns_number            7779
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_diffrn_reflns_theta_min         4.6308
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  0.945
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET)
(compiled Apr 21 2008,18:23:10)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             460
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.11(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         3939
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0298
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0388P)^2^+0.3169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0741
_refine_ls_wR_factor_ref         0.0840
_reflns_number_gt                3799
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_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol802572n_si_002.cif
_cod_data_source_block           compound4c
_cod_original_cell_volume        1097.97(8)
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               1503750