Enantioselective Construction of Tetrasubstituted Stereogenic Carbons through Brønsted Base Catalyzed Michael Reactions: α'-Hydroxy Enones as Key Enoate Equivalent.
Badiola, Eider; Fiser, Béla; Gómez-Bengoa, Enrique; Mielgo, Antonia; Olaizola, Iurre; Urruzuno, Iñaki; García, Jesús M; Odriozola, José M; Razkin, Jesús; Oiarbide, Mikel; Palomo, Claudio; Journal of the American Chemical Society  (2014) 141209140339003–; doi:10.1021/ja510603w

data_4123106
_publ_section_title
;
 Enantioselective Construction of Tetrasubstituted Stereogenic Carbons
 through Br\/onsted Base Catalyzed Michael Reactions: \a'-Hydroxy Enones
 as Key Enoate Equivalent.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141209140339003
_journal_paper_doi               10.1021/ja510603w
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C27 H32 Br1 N1 O4'
_chemical_formula_sum            'C27 H32 Br N O4'
_chemical_formula_weight         514.45
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-09-17T13:31:28-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7636(2)
_cell_length_b                   16.0522(4)
_cell_length_c                   28.0601(7)
_cell_measurement_reflns_used    5945
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.003
_cell_measurement_theta_min      2.508
_cell_measurement_wavelength     0.71073
_cell_volume                     2596.08(13)
_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(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2439
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -14.00   58.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204  -99.0000 -120.0000 72

  2 omega   35.00   83.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204 -178.0000 -120.0000 48

  3 omega  -52.00   67.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204    0.0000 -150.0000 119

  4 omega   65.00   95.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204   77.0000  150.0000 30

  5 omega   42.00   69.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204  178.0000   30.0000 27

  6 omega   -1.00   78.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204  -99.0000   90.0000 79

  7 omega  -14.00  105.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       26.6204   77.0000    0.0000 119

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0300897
_diffrn_orient_matrix_UB_12      -0.0396176
_diffrn_orient_matrix_UB_13      0.0093591
_diffrn_orient_matrix_UB_21      0.0133511
_diffrn_orient_matrix_UB_22      0.0178759
_diffrn_orient_matrix_UB_23      0.0229518
_diffrn_orient_matrix_UB_31      -0.1185188
_diffrn_orient_matrix_UB_32      -0.0080479
_diffrn_orient_matrix_UB_33      0.0049753
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Mo) X-ray micro-source'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.051
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            17657
_diffrn_reflns_theta_full        25.49
_diffrn_reflns_theta_max         25.49
_diffrn_reflns_theta_min         1.93
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.615
_exptl_absorpt_correction_T_max  0.949
_exptl_absorpt_correction_T_min  0.584
_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    1.316
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.8355
_exptl_crystal_size_mid          0.064
_exptl_crystal_size_min          0.0366
_refine_diff_density_max         0.769
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.066
_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 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.012(4), 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   0.013(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4805
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.053
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0404P)^2^+1.1535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0967
_reflns_number_gt                4318
_reflns_number_total             4805
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            ja510603w_si_001.cif
_cod_data_source_block           a2014334_iu1231
_cod_database_code               4123106