Base-Catalyzed Asymmetric α-Functionalization of 2-(Cyanomethyl)azaarene N-Oxides Leading to Quaternary Stereocenters.
Izquierdo, Joseba; Landa, Aitor; Bastida, Iñaki; López, Rosa; Oiarbide, Mikel; Palomo, Claudio; Journal of the American Chemical Society 138 (2016) 3282–3285; doi:10.1021/jacs.5b13385

data_4124940
_publ_section_title
;
 Base-Catalyzed Asymmetric \a-Functionalization of 2-(Cyanomethyl)azaarene
 N-Oxides Leading to Quaternary Stereocenters.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3282
_journal_page_last               3285
_journal_paper_doi               10.1021/jacs.5b13385
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C19 H20 N2 O3'
_chemical_formula_sum            'C19 H20 N2 O3'
_chemical_formula_weight         324.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-04-30T12:30:18-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 106.276(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.47304(18)
_cell_length_b                   15.3437(3)
_cell_length_c                   8.7824(2)
_cell_measurement_reflns_used    4907
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.266
_cell_measurement_theta_min      5.229
_cell_measurement_wavelength     1.54184
_cell_volume                     837.31(4)
_computing_cell_refinement       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_collection       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_reduction        'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_molecular_graphics    'Diamond v.3.2f (Crystal Impact GbR, 2008)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov et al, 2009)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega   32.00   63.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   37.0000    0.0000 31

  2 omega   70.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   37.0000    0.0000 31

  3 omega  -19.00   70.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.8256  -57.0000  -60.0000 89

  4 omega  -35.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.8256  -37.0000  120.0000 102

  5 omega   16.00  111.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   57.0000  -90.0000 95

  6 omega -107.00  -34.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   77.0000  150.0000 73

  7 omega   39.00   68.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   90.0000 29

  8 omega   48.00  115.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000   60.0000 67

  9 omega   89.00  148.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000   90.0000 59

 10 omega   39.00   67.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   60.0000 28

 11 omega   40.00   67.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -150.0000 27

 12 omega   97.00  142.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000   60.0000 45

 13 omega   41.00   69.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000    0.0000 28

 14 omega   37.00   68.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   30.0000 31

 15 omega   96.00  158.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -30.0000 62

 16 omega   38.00  113.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 75

 17 omega  106.00  132.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -180.0000 26

 18 omega   36.00   69.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  150.0000 33

 19 omega   49.00  103.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -180.0000 54

 20 omega   85.00  137.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000   30.0000 52

 21 omega   36.00   69.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -180.0000 33

 22 omega   94.00  157.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -150.0000 63

 23 omega   37.00   65.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -120.0000 28

 24 omega   37.00   63.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  -60.0000 26

 25 omega  123.00  155.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -180.0000 32

 26 omega   67.00  116.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000  -90.0000 49

 27 omega  -96.00  -70.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  125.0000  -60.0000 26

 28 omega  -28.00   -2.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  125.0000  -60.0000 26

 29 omega  -61.00  -11.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000  120.0000 50

 30 omega   56.00  110.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  -90.0000 54

 31 omega   77.00  102.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -30.0000 25

 32 omega   82.00  139.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -15.0000 -180.0000 57
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0721018
_diffrn_orient_matrix_UB_12      -0.0942336
_diffrn_orient_matrix_UB_13      0.0172997
_diffrn_orient_matrix_UB_21      -0.0657251
_diffrn_orient_matrix_UB_22      -0.0106613
_diffrn_orient_matrix_UB_23      -0.1814351
_diffrn_orient_matrix_UB_31      0.2283355
_diffrn_orient_matrix_UB_32      -0.0329595
_diffrn_orient_matrix_UB_33      0.0088459
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            7348
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.979
_diffrn_reflns_theta_min         5.247
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.712
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_correction_T_min  0.827
_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.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             344
_exptl_crystal_size_max          0.4932
_exptl_crystal_size_mid          0.3023
_exptl_crystal_size_min          0.0661
_refine_diff_density_max         0.305
_refine_diff_density_min         -0.172
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (100%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2011).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-26. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.08(10), which together with Flack parameter 
value, indicate that the absolute structure has sureley been determined 
correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717

;
_refine_ls_abs_structure_Flack   -0.06(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         3220
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0368
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0463P)^2^+0.2459P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0936
_refine_ls_wR_factor_ref         0.0944
_reflns_number_gt                3151
_reflns_number_total             3220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b13385_si_001.cif
_cod_data_source_block           a2014315_aitor10
_cod_depositor_comments
'Adding full bibliography for 4124940--4124941.cif.'
_cod_original_cell_volume        837.31(3)
_cod_database_code               4124940