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_4126607
_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         'C29 H28 N2 O3 S1'
_chemical_formula_sum            'C29 H28 N2 O3 S'
_chemical_formula_weight         484.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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
_audit_creation_date             2017-07-28T12:21:15-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.87209(18)
_cell_length_b                   14.5091(2)
_cell_length_c                   24.6499(3)
_cell_measurement_reflns_used    26108
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.959
_cell_measurement_theta_min      3.481
_cell_measurement_wavelength     1.54184
_cell_volume                     4961.32(11)
_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 1
_diffrn_measured_fraction_theta_max 1
_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   -106.00 -18.00   1.00    2.50    --  -41.08 -57.00-120.00   88
  2  \w    -15.00  57.00   1.00    2.50    --   41.08 -38.00  60.00   72
  3  \w   -158.00-128.00   1.00   10.00    --  -83.00-125.00 -30.00   30
  4  \w     32.00  66.00   1.00   10.00    --  108.36 -30.00  90.00   34
  5  \w     34.00  68.00   1.00   10.00    --  108.36 -30.00-120.00   34
  6  \w     33.00  66.00   1.00   10.00    --  108.36 -30.00-150.00   33
  7  \w     32.00  69.00   1.00   10.00    --  108.36 -30.00-180.00   37
  8  \w     40.00 102.00   1.00   10.00    --  108.36 -94.00  60.00   62
  9  \w     33.00  67.00   1.00   10.00    --  108.36 -30.00 -90.00   34
 10  \w     33.00  69.00   1.00   10.00    --  108.36 -30.00 -60.00   36
 11  \w     40.00  65.00   1.00   10.00    --  108.36 -45.00  30.00   25
 12  \w     31.00  67.00   1.00   10.00    --  108.36 -30.00 150.00   36
 13  \w     40.00  77.00   1.00   10.00    --  108.36 -94.00-180.00   37
 14  \w     28.00 105.00   1.00   10.00    --  108.36 -94.00 120.00   77
 15  \w     31.00  93.00   1.00    2.50    --   41.08  38.00-150.00   62
 16  \w      3.00  95.00   1.00    2.50    --   41.08-125.00  30.00   92
 17  \w     87.00 114.00   1.00    2.50    --   41.08  38.00-120.00   27
 18  \w   -122.00 -94.00   1.00   10.00    --  -83.00 144.00-107.00   28
 19  \w    -68.00 -10.00   1.00   10.00    --  -83.00  30.00 120.00   58
 20  \w     30.00  64.00   1.00   10.00    --  108.36 -30.00  30.00   34
 21  \w    111.00 156.00   1.00   10.00    --  108.36  15.00 -30.00   45
 22  \w     78.00 108.00   1.00   10.00    --  108.36  15.00 -30.00   30
 23  \w     62.00 116.00   1.00   10.00    --  108.36-125.00-120.00   54
 24  \w     44.00  87.00   1.00   10.00    --  108.36 -94.00-120.00   43
 25  \w     39.00  64.00   1.00   10.00    --  108.36 -30.00   0.00   25
 26  \w    122.00 156.00   1.00   10.00    --  108.36  45.00-180.00   34
 27  \w     58.00 122.00   1.00   10.00    --  108.36-125.00 -30.00   64
 28  \w     79.00 147.00   1.00   10.00    --  108.36  61.00  30.00   68
 29  \w     43.00  74.00   1.00   10.00    --  108.36 -94.00 -30.00   31
 30  \w     32.00  67.00   1.00   10.00    --  108.36 -30.00  60.00   35
 31  \w     49.00 102.00   1.00   10.00    --  108.36 -94.00   0.00   53
 32  \w     32.00  63.00   1.00   10.00    --  108.36 -30.00 120.00   31
 33  \w    -68.00 -43.00   1.00   10.00    --  -83.00  30.00 120.00   25
 34  \w   -115.00 -11.00   1.00    2.50    --  -41.08 -57.00  30.00  104
 35  \w   -115.00 -11.00   1.00    2.50    --  -41.08 -57.00 120.00  104
 36  \w   -120.00  -7.00   1.00    2.50    --  -41.08 -77.00 -60.00  113
 37  \w    -67.00  35.00   1.00    2.50    --  -41.08  38.00 -90.00  102
 38  \w   -120.00  -7.00   1.00    2.50    --  -41.08 -77.00 120.00  113
 39  \w   -120.00  -7.00   1.00    2.50    --  -41.08 -77.00-150.00  113
 40  \w   -120.00  -7.00   1.00    2.50    --  -41.08 -77.00   0.00  113
 41  \w   -162.00 -49.00   1.00   10.00    --  -83.00 -77.00   0.00  113
 42  \w   -162.00 -49.00   1.00   10.00    --  -83.00 -77.00 -90.00  113
 43  \w   -162.00 -49.00   1.00   10.00    --  -83.00 -77.00-150.00  113
 44  \w   -162.00 -49.00   1.00   10.00    --  -83.00 -77.00  90.00  113
 45  \w   -162.00 -49.00   1.00   10.00    --  -83.00 -77.00 150.00  113
 46  \w     78.00 158.00   1.00   10.00    --  108.36  61.00 -30.00   80
 47  \w     78.00 158.00   1.00   10.00    --  108.36  61.00-180.00   80
 48  \w     81.00 158.00   1.00   10.00    --  108.36  45.00  90.00   77
 49  \w     81.00 158.00   1.00   10.00    --  108.36  45.00-120.00   77
 50  \w     78.00 158.00   1.00   10.00    --  108.36  30.00 150.00   80
;
_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      0.0044123
_diffrn_orient_matrix_UB_12      0.0762004
_diffrn_orient_matrix_UB_13      -0.0434831
_diffrn_orient_matrix_UB_21      -0.0138492
_diffrn_orient_matrix_UB_22      -0.0729523
_diffrn_orient_matrix_UB_23      -0.0447571
_diffrn_orient_matrix_UB_31      -0.1100353
_diffrn_orient_matrix_UB_32      0.0121076
_diffrn_orient_matrix_UB_33      0.0039155
_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  0.0786
_diffrn_reflns_av_unetI/netI     0.0926
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            88931
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.986
_diffrn_reflns_theta_min         3.535
_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    1.426
_exptl_absorpt_correction_T_max  0.946
_exptl_absorpt_correction_T_min  0.679
_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. Reid.
(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    1.298
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.321
_exptl_crystal_size_mid          0.297
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.4
_refine_diff_density_min         -0.37
_refine_diff_density_rms         0.053
_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, 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 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=0.016(7), 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   0.013(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         9401
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0614P)^2^+3.8723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1375
_refine_ls_wR_factor_ref         0.1457
_reflns_number_gt                7855
_reflns_number_total             9401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b09124_si_002.cif
_cod_data_source_block           a20170193_srp606
_cod_original_cell_volume        4961.31(11)
_cod_database_code               4126607