Enantioselective Conjugate Addition of Donor-Acceptor Hydrazones to α,β-Unsaturated Aldehydes through Formal Diaza-Ene Reaction: Access to 1,4-Dicarbonyl Compounds
Maitane Fernández; Uxue Uria; Jose L. Vicario; Efraím Reyes; Luisa Carrillo; Journal of the American Chemical Society 134 (2012) 11872–11875; doi:10.1021/ja3041042

data_4118340
_publ_contact_author_address
;
Departamento de Quimica Organica II, Facultad de Ciencia y Tecnologia,
Universidad del Pais Vasco/Euskal Herriko Unibertsitatea. P.O. Box 644,
48080 Bilbao, Spain
;
_publ_contact_author_email       joseluis.vicario@ehu.es
_publ_contact_author_fax         (+34)946012748
_publ_contact_author_name        'Jose L. Vicario'
_publ_contact_author_phone       (+34)946015454
_publ_section_title
;
 Enantioselective Conjugate Addition of Donor-Acceptor Hydrazones to
 \a,\b-Unsaturated Aldehydes through Formal Diaza-Ene Reaction: Access to
 1,4-Dicarbonyl Compounds
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11872
_journal_page_last               11875
_journal_paper_doi               10.1021/ja3041042
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C16 H21 N3 O3'
_chemical_formula_sum            'C16 H21 N3 O3'
_chemical_formula_weight         303.36
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      5
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4
_audit_creation_date             2012-04-28T11:22:11-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90.2410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.6846(4)
_cell_length_b                   8.38130(10)
_cell_length_c                   6.96910(10)
_cell_measurement_reflns_used    10163
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.9968
_cell_measurement_theta_min      3.3097
_cell_measurement_wavelength     1.54184
_cell_volume                     1558.64(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    'SIR92 (Altomare et al, 1993)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -56.00  -21.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756   57.0000   60.0000 35

  2 omega   19.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   38.0000 -120.0000 96

  3 omega   62.00   88.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -126.0000 -114.0000 26

  4 omega   39.00   68.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   90.0000 29

  5 omega   38.00   65.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000    0.0000 27

  6 omega   36.00   69.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   30.0000 33

  7 omega   55.00  120.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -126.0000   65.0000 65

  8 omega   30.00   55.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  120.0000 25

  9 omega   39.00   65.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000    0.0000 26

 10 omega   37.00   66.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   60.0000 29

 11 omega   87.00  116.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -61.0000  150.0000 29

 12 omega  -42.00   -6.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756   57.0000  -90.0000 36

 13 omega   34.00   69.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000    0.0000 35

 14 omega   37.00   80.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  -60.0000 43

 15 omega   35.00   62.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -60.0000 27

 16 omega   25.00   51.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  150.0000 26

 17 omega   63.00   89.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  150.0000 26

 18 omega   34.00   67.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  150.0000 33

 19 omega  -51.00   -7.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756  126.0000  -37.0000 44

 20 omega  -87.00  -59.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756  126.0000  -37.0000 28

 21 omega  -24.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756  -38.0000   60.0000 91

 22 omega    5.00   44.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000    0.0000 39

 23 omega   31.00   68.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -90.0000 37

 24 omega   31.00   67.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -180.0000 36

 25 omega   36.00   67.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -30.0000 31

 26 omega   35.00   61.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -150.0000 26

 27 omega   58.00  115.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -90.0000 57

 28 omega   96.00  133.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000  120.0000 37

 29 omega   39.00   66.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  150.0000 27

 30 omega   31.00   63.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000 -120.0000 32

 31 omega   89.00  115.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -145.0000   49.0000 26

 32 omega  111.00  152.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000 -180.0000 41

 33 omega   35.00  114.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000   60.0000 79

 34 omega  -98.00   -2.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756  125.0000    0.0000 96

 35 omega  -74.00   38.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756   77.0000  -90.0000 112

 36 omega -119.00   -7.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756  -77.0000  -60.0000 112

 37 omega -114.00  -62.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -40.5756 -145.0000   78.0000 52

 38 omega    7.00  119.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   77.0000 -120.0000 112

 39 omega   11.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   57.0000   90.0000 104

 40 omega    7.00  119.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   77.0000  150.0000 112

 41 omega   11.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   57.0000  -30.0000 104

 42 omega   11.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.5756   57.0000   30.0000 104

 43 omega -162.00  -49.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -150.0000 113

 44 omega -162.00  -49.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  150.0000 113

 45 omega -162.00  -49.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -30.0000 113

 46 omega -162.00  -49.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   30.0000 113

 47 omega -162.00  -49.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 113

 48 omega   78.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000   90.0000 80

 49 omega   78.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000  150.0000 80

 50 omega   78.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000    0.0000 80

 51 omega   47.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   15.0000  -60.0000 111

 52 omega   78.00  158.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000   60.0000 80

 53 omega   30.00  142.00   1.0000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000   90.0000 112

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0143147
_diffrn_orient_matrix_UB_12      0.0078819
_diffrn_orient_matrix_UB_13      -0.2141338
_diffrn_orient_matrix_UB_21      -0.0557995
_diffrn_orient_matrix_UB_22      -0.0150356
_diffrn_orient_matrix_UB_23      0.0531102
_diffrn_orient_matrix_UB_31      -0.0039837
_diffrn_orient_matrix_UB_32      0.182995
_diffrn_orient_matrix_UB_33      0.013739
_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  0.0486
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            3364
_diffrn_reflns_theta_full        69.97
_diffrn_reflns_theta_max         69.97
_diffrn_reflns_theta_min         3.31
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.74
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.83939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
        (compiled Jan 23 2012,18:06:46)
        empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       prism
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.22
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (87%).
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 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.16(6), 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   0.08(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3364
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.037
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0761P)^2^+0.2670P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1019
_refine_ls_wR_factor_ref         0.1034
_reflns_number_gt                3210
_reflns_number_total             3364
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            ja3041042_si_001.cif
_cod_data_source_block           mf783
_cod_database_code               4118340