Asymmetric Synthesis of Amino-Bis-Pyrazolone Derivatives via an Organocatalytic Mannich Reaction.
Chauhan, Pankaj; Mahajan, Suruchi; Kaya, Ugur; Peuronen, Anssi; Rissanen, Kari; Enders, Dieter; The Journal of organic chemistry  (2017) –; doi:10.1021/acs.joc.7b01113

data_4032577
_publ_section_title
;
 Asymmetric Synthesis of Amino-Bis-Pyrazolone Derivatives via an
 Organocatalytic Mannich Reaction.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.7b01113
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H31 N5 O4'
_chemical_formula_sum            'C33 H31 N5 O4'
_chemical_formula_weight         561.63
_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_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             2017-03-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.8024(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.48005(13)
_cell_length_b                   24.7093(3)
_cell_length_c                   12.42655(18)
_cell_measurement_reflns_used    22592
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      76.5700
_cell_measurement_theta_min      3.8190
_cell_volume                     2966.42(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3953
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -116.00 -18.00   1.00    3.50    --  -41.90 -37.00  30.00   98
  2  \w   -116.00 -18.00   1.00    3.50    --  -41.90 -37.00 -60.00   98
  3  \w   -122.00  -1.00   1.00    3.50    --  -41.90 -19.00 120.00  121
  4  \w      1.00  83.00   1.00    3.50    --   41.90 -99.00  30.00   82
  5  \w     20.00  46.00   1.00    3.50    --   54.00  81.00 -73.48   26
  6  \w     40.00 143.00   1.00    3.50    --   70.00  64.00 -20.92  103
  7  \w     37.00 146.00   1.00    3.50    --   70.00  77.00 -77.29  109
  8  \w     51.00 156.00   1.00   17.50    --   82.00  72.00 -39.72  105
  9  \w     65.00 166.00   1.00   17.50    --   94.00  62.00 -87.05  101
 10  \w    100.00 178.00   1.00   17.50    --  112.00 111.00 120.00   78
 11  \w     36.00 116.00   1.00   17.50    --  112.00-111.00 -60.00   80
 12  \w     36.00 116.00   1.00   17.50    --  112.00-111.00 150.00   80
 13  \w     79.00 178.00   1.00   17.50    --  112.00  77.00 -30.00   99
 14  \w     83.00 178.00   1.00   17.50    --  112.00  61.00 -30.00   95
 15  \w     79.00 178.00   1.00   17.50    --  112.00  77.00 -60.00   99
 16  \w     36.00 116.00   1.00   17.50    --  112.00-111.00  60.00   80
 17  \w     79.00 178.00   1.00   17.50    --  112.00  77.00  30.00   99
 18  \w     83.00 178.00   1.00   17.50    --  112.00  61.00   0.00   95
 19  \w     79.00 178.00   1.00   17.50    --  112.00  77.00 -90.00   99
 20  \w     57.00 151.00   1.00   17.50    --  112.00 178.00-180.00   94
 21  \w     81.00 178.00   1.00   17.50    --  112.00  71.00   2.85   97
 22  \w     16.00  46.00   1.00    3.50    --   50.00  81.00 163.30   30
 23  \w     21.00  49.00   1.00    3.50    --   54.00  78.00-125.11   28
 24  \w     21.00  49.00   1.00    3.50    --   54.00  78.00  34.55   28
 25  \w     30.00 137.00   1.00    3.50    --   62.00  75.00-167.05  107
 26  \w     33.00 142.00   1.00    3.50    --   66.00  77.00  79.26  109
 27  \w     38.00 145.00   1.00    3.50    --   70.00  75.00 145.40  107
 28  \w     83.00 178.00   1.00   17.50    --  112.00  61.00  90.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1418874000
_diffrn_orient_matrix_UB_12      -0.0193456000
_diffrn_orient_matrix_UB_13      -0.0047734000
_diffrn_orient_matrix_UB_21      -0.0687081000
_diffrn_orient_matrix_UB_22      0.0202034000
_diffrn_orient_matrix_UB_23      -0.1267870000
_diffrn_orient_matrix_UB_31      0.0241727000
_diffrn_orient_matrix_UB_32      -0.0557476000
_diffrn_orient_matrix_UB_33      -0.0444117000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            45844
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.000
_diffrn_reflns_theta_min         3.578
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.683
_exptl_absorpt_correction_T_max  0.937
_exptl_absorpt_correction_T_min  0.803
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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_colour_primary    colourless
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.145
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.171
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 4882 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     885
_refine_ls_number_reflns         11547
_refine_ls_number_restraints     147
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0325
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0516P)^2^+0.1707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0831
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                10791
_reflns_number_total             11547
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01113_si_002.cif
_cod_data_source_block           8a
_cod_original_cell_volume        2966.42(7)
_cod_database_code               4032577
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C33 H31 N5 O4'
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C35D-C30D = C35D-C34D
 1.39 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C30C \\sim C30E \\sim C31C \\sim C31E \\sim C32C \\sim C32E \\sim C33C \\sim
C33E \\sim C34C \\sim C34E \\sim C35C: within 2A with sigma of 0.008 and sigma
for terminal atoms of 0.004
C30D \\sim C31D \\sim C32D \\sim C33D \\sim C34D \\sim C35D: within 2A with
sigma of 0.008 and sigma for terminal atoms of 0.004
C30E \\sim C31C \\sim C31E \\sim C32C \\sim C32E \\sim C33C \\sim C33E \\sim
C34C \\sim C34E \\sim C35C \\sim C35E: within 2A with sigma of 0.008 and sigma
for terminal atoms of 0.004
C30F \\sim C31F \\sim C32F \\sim C33F \\sim C34F \\sim C35F: within 2A with
sigma of 0.008 and sigma for terminal atoms of 0.004
4. Others
 Sof(C30F)=Sof(C31F)=Sof(H31F)=Sof(C32F)=Sof(H32F)=Sof(C33F)=Sof(H33F)=
 Sof(C34F)=Sof(H34F)=Sof(C35F)=Sof(H35F)=1-FVAR(1)
 Sof(C30E)=Sof(C31E)=Sof(H31E)=Sof(C32E)=Sof(H32E)=Sof(C33E)=Sof(H33E)=
 Sof(C34E)=Sof(H34E)=Sof(C35E)=Sof(H35E)=FVAR(1)
 Sof(C30D)=Sof(C31D)=Sof(H31D)=Sof(C32D)=Sof(H32D)=Sof(C33D)=Sof(H33D)=
 Sof(C34D)=Sof(H34D)=Sof(C35D)=Sof(H35D)=1-FVAR(2)
 Sof(C30C)=Sof(C31C)=Sof(H31C)=Sof(C32C)=Sof(H32C)=Sof(C33C)=Sof(H33C)=
 Sof(C34C)=Sof(H34C)=Sof(C35C)=Sof(H35C)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C31C(H31C),
 C31D(H31D), C32C(H32C), C32D(H32D), C33C(H33C), C33D(H33D), C34C(H34C),
 C34D(H34D), C35C(H35C), C35D(H35D), C37A(H37A), C38A(H38A), C39A(H39A),
 C40A(H40A), C41A(H41A), C21B(H21B), C22B(H22B), C23B(H23B), C24B(H24B),
 C25B(H25B), C31E(H31E), C31F(H31F), C32E(H32E), C32F(H32F), C33E(H33E),
 C33F(H33F), C34E(H34E), C34F(H34F), C35E(H35E), C35F(H35F), C37B(H37B),
 C38B(H38B), C39B(H39B), C40B(H40B), C41B(H41B)
5.b Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C26A(H26A,
 H26B,H26C), C27A(H27A,H27B,H27C), C16B(H16D,H16E,H16F), C17B(H17D,H17E,H17F),
 C18B(H18D,H18E,H18F), C26B(H26D,H26E,H26F), C27B(H27D,H27E,H27F)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.184
_oxdiff_exptl_absorpt_empirical_full_min 0.828