Catalytic Asymmetric Synthesis of Quaternary Barbituric Acids.
Del Pozo, Sandra; Vera, Silvia; Oiarbide, Mikel; Palomo, Claudio; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b09124

data_4126608
_publ_section_title
;
 Catalytic Asymmetric Synthesis of Quaternary Barbituric Acids.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b09124
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C17 H20 N2 O5'
_chemical_formula_sum            'C17 H20 N2 O5'
_chemical_formula_weight         332.35
_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             2017-07-27T14:04:35-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 96.8558(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.83592(12)
_cell_length_b                   6.02967(6)
_cell_length_c                   13.59401(15)
_cell_measurement_reflns_used    12014
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.007
_cell_measurement_theta_min      4.501
_cell_measurement_wavelength     1.54184
_cell_volume                     800.460(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -33.00  34.00   1.00    1.00    --  -41.33  38.00 150.00   67
  2  \w   -111.00 -38.00   1.00    1.00    --  -41.33 -77.00  90.00   73
  3  \w      8.00  98.00   1.00    1.00    --   41.33-125.00 -30.00   90
  4  \w      8.00 107.00   1.00    1.00    --   41.33  77.00-120.00   99
  5  \w    -38.00 -12.00   1.00    1.00    --  -83.00 125.00-150.00   26
  6  \w   -116.00 -86.00   1.00    1.00    --  -83.00 125.00-150.00   30
  7  \w     67.00 100.00   1.00    1.00    --  108.36 -94.00  30.00   33
  8  \w     41.00  91.00   1.00    1.00    --  108.36 -94.00-180.00   50
  9  \w     30.00  69.00   1.00    1.00    --  108.36 -30.00 150.00   39
 10  \w     81.00 154.00   1.00    1.00    --  108.36  45.00 150.00   73
 11  \w     34.00  59.00   1.00    1.00    --  108.36 -45.00 -90.00   25
 12  \w     26.00 147.00   1.00    1.00    --  108.36 -15.00 -30.00  121
 13  \w     29.00 108.00   1.00    1.00    --  108.36 -94.00  90.00   79
 14  \w    104.00 132.00   1.00    1.00    --  108.36 125.00 120.00   28
 15  \w     81.00 111.00   1.00    1.00    --  108.36  45.00 -90.00   30
 16  \w     35.00  61.00   1.00    1.00    --  108.36 -45.00  90.00   26
 17  \w     38.00  64.00   1.00    1.00    --  108.36 -30.00  90.00   26
 18  \w     47.00  83.00   1.00    1.00    --  108.36-125.00 -90.00   36
 19  \w     91.00 119.00   1.00    1.00    --  108.36-125.00 -90.00   28
 20  \w     83.00 152.00   1.00    1.00    --  108.36  45.00  90.00   69
 21  \w     39.00  64.00   1.00    1.00    --  108.36 -45.00  60.00   25
 22  \w     80.00 157.00   1.00    1.00    --  108.36  61.00 -30.00   77
 23  \w    -12.00  48.00   1.00    1.00    --  -41.33   0.00-150.00   60
 24  \w    -38.00 -11.00   1.00    1.00    --  -83.00  30.00  90.00   27
 25  \w     34.00  66.00   1.00    1.00    --  108.36-125.00 -60.00   32
 26  \w     30.00  55.00   1.00    1.00    --  108.36 -30.00 -30.00   25
 27  \w     30.00  55.00   1.00    1.00    --  108.36 -30.00   0.00   25
 28  \w     30.00  55.00   1.00    1.00    --  108.36 -30.00-120.00   25
 29  \w     96.00 122.00   1.00    1.00    --  108.36-125.00 -60.00   26
 30  \w     32.00  58.00   1.00    1.00    --  108.36 -30.00 120.00   26
 31  \w     54.00 109.00   1.00    1.00    --  108.36 -94.00 -90.00   55
 32  \w     92.00 139.00   1.00    1.00    --  108.36 -77.00 -90.00   47
 33  \w   -120.00  -8.00   1.00    1.00    --  -41.33 -77.00 -90.00  112
 34  \w   -124.00 -79.00   1.00    1.00    --  -41.33 -99.00-120.00   45
 35  \w      8.00 120.00   1.00    1.00    --   41.33  77.00   0.00  112
 36  \w      8.00 120.00   1.00    1.00    --   41.33  77.00  90.00  112
 37  \w     12.00 115.00   1.00    1.00    --   41.33  57.00 150.00  103
 38  \w      2.00  99.00   1.00    1.00    --   41.33-125.00 150.00   97
 39  \w   -162.00 -49.00   1.00    1.00    --  -83.00 -77.00 -90.00  113
 40  \w   -157.00 -53.00   1.00    1.00    --  -83.00 -61.00  60.00  104
 41  \w   -162.00 -49.00   1.00    1.00    --  -83.00 -77.00   0.00  113
 42  \w   -162.00 -49.00   1.00    1.00    --  -83.00 -77.00 120.00  113
 43  \w   -162.00 -49.00   1.00    1.00    --  -83.00 -77.00-150.00  113
 44  \w   -157.00 -53.00   1.00    1.00    --  -83.00 -61.00 150.00  104
 45  \w     78.00 158.00   1.00    1.00    --  108.36  61.00  30.00   80
 46  \w     34.00  77.00   1.00    1.00    --  108.36 -45.00 -60.00   43
 47  \w     78.00 158.00   1.00    1.00    --  108.36  61.00 -60.00   80
 48  \w     24.00 109.00   1.00    1.00    --  108.36 -94.00 -60.00   85
;
_diffrn_measurement_device       'four-circle\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.089899
_diffrn_orient_matrix_UB_12      0.155703
_diffrn_orient_matrix_UB_13      0.054707
_diffrn_orient_matrix_UB_21      -0.005201
_diffrn_orient_matrix_UB_22      -0.1756373
_diffrn_orient_matrix_UB_23      0.0817884
_diffrn_orient_matrix_UB_31      0.1294899
_diffrn_orient_matrix_UB_32      0.1011157
_diffrn_orient_matrix_UB_33      0.0578194
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0248
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14405
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.975
_diffrn_reflns_theta_min         3.274
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.854
_exptl_absorpt_correction_T_max  0.903
_exptl_absorpt_correction_T_min  0.851
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             352
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.151
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.151
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (99%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2010).
 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 10-90. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=0.03(5), 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
Dolomanov, O.V. (2009) OLEX2, J. Appl. Cryst., 42, 339-341. 
Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13.
Spek, A.L. (2009). Acta Cryst. D65, 148-155.
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   0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.03
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3010
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.03
_refine_ls_R_factor_all          0.024
_refine_ls_R_factor_gt           0.0235
_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^)+(0.0350P)^2^+0.1097P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.06
_refine_ls_wR_factor_ref         0.0604
_reflns_number_gt                2960
_reflns_number_total             3010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09124_si_003.cif
_cod_data_source_block           a20160137_srp137col1
_cod_original_cell_volume        800.461(15)
_cod_database_code               4126608