Cu/Fe-cocatalyzed Meyer-Schuster-like rearrangement of propargylic amines: direct access to E-β-aminoacryaldehydes.
Chen, Ming; Peng, Jiangling; Mao, Tingting; Huang, Jinbo; Organic letters 16 (2014) 6286–6289; doi:10.1021/ol5029805

data_1518384
_publ_section_title
;
 Cu/Fe-cocatalyzed Meyer-Schuster-like rearrangement of propargylic
 amines: direct access to E-\b-aminoacryaldehydes.
;
_journal_issue                   24
_journal_name_full               'Organic letters'
_journal_page_first              6286
_journal_page_last               6289
_journal_paper_doi               10.1021/ol5029805
_journal_volume                  16
_journal_year                    2014
_chemical_formula_moiety         'C16 H14 Br N O'
_chemical_formula_sum            'C16 H14 Br N O'
_chemical_formula_weight         316.19
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-03-19
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                101.320(3)
_cell_angle_beta                 91.514(3)
_cell_angle_gamma                96.308(3)
_cell_formula_units_Z            2
_cell_length_a                   6.4762(2)
_cell_length_b                   8.5838(3)
_cell_length_c                   13.2261(4)
_cell_measurement_reflns_used    7877
_cell_measurement_temperature    293
_cell_measurement_theta_max      66.4850
_cell_measurement_theta_min      3.4150
_cell_volume                     715.71(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      293
_diffrn_detector_area_resol_mean 10.4015
_diffrn_measured_fraction_theta_full 0.9943
_diffrn_measured_fraction_theta_max 0.9429
_diffrn_measurement_details
;
  1 omega   11.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   57.0000   30.0000 44

  2 omega   87.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   57.0000   30.0000 26

  3 omega   15.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   38.0000 -120.0000 55

  4 omega    7.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   77.0000   90.0000 38

  5 omega    2.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890  -99.0000  150.0000 81

  6 omega   66.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   77.0000   90.0000 54

  7 omega   54.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   77.0000  -90.0000 66

  8 omega    8.00   47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9890   77.0000  -90.0000 39

  9 omega  -46.00  -14.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -48.0000  -83.0000   18.9249 32

 10 omega  -42.00  -17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -52.0000  -85.0000 -154.5901 25

 11 omega  -46.00  -21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -56.0000  -84.0000  -71.9646 25

 12 omega  -46.00  -21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -56.0000  -84.0000 -124.8621 25

 13 omega  110.00  136.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  162.5443 26

 14 omega   27.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  162.5443 27

 15 omega   33.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   79.0000  102.9638 31

 16 omega  101.00  141.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   79.0000  102.9638 40

 17 omega   34.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   78.0000   88.2155 26

 18 omega  -70.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -76.0000  -71.0000  -37.8754 26

 19 omega  -72.00  -43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000 -120.0000 29

 20 omega  -87.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -73.0000    6.8565 43

 21 omega -144.00 -116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000  120.0000 28

 22 omega  -70.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000 -150.0000 26

 23 omega  -70.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000 -180.0000 26

 24 omega  -73.00  -47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000  -60.0000 26

 25 omega -120.00  -93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  125.0000  120.0000 27

 26 omega  -70.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000   30.0000 26

 27 omega  -69.00  -43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -77.0000  -77.0000  120.0000 26

 28 omega   59.00  162.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000    0.0000 103

 29 omega   63.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   61.0000  -90.0000 83

 30 omega   19.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -94.0000  150.0000 64

 31 omega  111.00  169.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   30.0000 58

 32 omega   66.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   30.0000 39

 33 omega    9.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -86.0000  -11.8896 109

 34 omega  115.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -180.0000 34

 35 omega   60.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -180.0000 48

 36 omega   24.00  129.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -92.0000 -145.5415 105

 37 omega   92.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  120.0000 28

 38 omega   59.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  120.0000 26

 39 omega  107.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -30.0000 31

 40 omega   62.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -30.0000 27

 41 omega   20.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000   30.0000 54

 42 omega   59.00  168.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -60.0000 109

 43 omega   59.00  169.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  150.0000 110

 44 omega   59.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   90.0000 89

 45 omega   61.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -150.0000 88

 46 omega   59.00  127.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   60.0000 68

 47 omega   38.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000 -120.0000 36
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0052681000
_diffrn_orient_matrix_UB_12      0.0691352000
_diffrn_orient_matrix_UB_13      0.1168178000
_diffrn_orient_matrix_UB_21      -0.1688938000
_diffrn_orient_matrix_UB_22      -0.1345077000
_diffrn_orient_matrix_UB_23      0.0133475000
_diffrn_orient_matrix_UB_31      0.1698948000
_diffrn_orient_matrix_UB_32      -0.1053438000
_diffrn_orient_matrix_UB_33      0.0179070000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10364
_diffrn_reflns_theta_full        66.59
_diffrn_reflns_theta_max         66.59
_diffrn_reflns_theta_min         3.41
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.835
_exptl_absorpt_correction_T_max  0.778
_exptl_absorpt_correction_T_min  0.588
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             320
_exptl_crystal_size_max          0.3875
_exptl_crystal_size_mid          0.304
_exptl_crystal_size_min          0.1445
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2470
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0324
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0528P)^2^+0.1635P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0890
_reflns_number_gt                2294
_reflns_number_total             2470
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol5029805_si_001.cif
_cod_data_source_block           exp_638
_cod_depositor_comments          'Adding full bibliography for 1518384.cif.'
_cod_original_cell_volume        715.72(4)
_cod_database_code               1518384
_chemical_oxdiff_formula         c16h14n1o1br1
_reflns_odcompleteness_completeness 99.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     62.30
_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.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19)
2.b Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;