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_4032578
_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         'C27 H29 N5 O5'
_chemical_formula_sum            'C27 H29 N5 O5'
_chemical_formula_weight         503.55
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 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                111.076(7)
_cell_angle_beta                 99.361(5)
_cell_angle_gamma                92.468(5)
_cell_formula_units_Z            2
_cell_length_a                   6.5282(4)
_cell_length_b                   14.5999(11)
_cell_length_c                   14.9551(10)
_cell_measurement_reflns_used    8697
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      76.2670
_cell_measurement_theta_min      5.3340
_cell_volume                     1304.31(17)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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      0.00  26.00   2.00   10.00    --   38.00  93.00 -79.54   13
  2  \w    -70.00  30.00   2.00   10.00    --  -41.78  57.00 150.00   50
  3  \w   -114.00 -14.00   2.00   10.00    --  -41.78 -57.00  60.00   50
  4  \w   -114.00 -14.00   2.00   10.00    --  -41.78 -57.00 -30.00   50
  5  \w   -114.00 -14.00   2.00   10.00    --  -41.78 -57.00 150.00   50
  6  \w    -74.00  34.00   2.00   10.00    --  -41.78  77.00-120.00   54
  7  \w     23.00  97.00   2.00   10.00    --   41.78-125.00  60.00   37
  8  \w     13.00  47.00   2.00   10.00    --   46.00  79.00 159.52   17
  9  \w     21.00  47.00   2.00   10.00    --   54.00  79.00-136.01   13
 10  \w     20.00  46.00   2.00   10.00    --   54.00  81.00 -22.28   13
 11  \w     20.00  46.00   2.00   10.00    --   54.00  81.00 -80.66   13
 12  \w     21.00  49.00   2.00   10.00    --   54.00  78.00  72.23   14
 13  \w     25.00 133.00   2.00   10.00    --   58.00  77.00 172.86   54
 14  \w     26.00 132.00   2.00   10.00    --   58.00  75.00  30.86   53
 15  \w     29.00 137.00   2.00   10.00    --   62.00  77.00 -13.47   54
 16  \w     34.00 140.00   2.00   10.00    --   66.00  75.00 102.52   53
 17  \w     34.00 140.00   2.00   10.00    --   66.00  75.00 -74.45   53
 18  \w     39.00 143.00   2.00   10.00    --   70.00  69.00  54.83   52
 19  \w     38.00 146.00   2.00   10.00    --   70.00  76.00 179.03   54
 20  \w     44.00 146.00   2.00   10.00    --   74.00  65.00  79.45   51
 21  \w     43.00 147.00   2.00   10.00    --   74.00  70.00 -37.19   52
 22  \w     43.00 147.00   2.00   10.00    --   74.00  69.00-134.09   52
 23  \w     54.00  88.00   2.00   35.00    --   82.00  60.00 151.19   17
 24  \w    104.00 152.00   2.00   35.00    --   86.00  72.00  86.87   24
 25  \w     55.00  83.00   2.00   35.00    --   86.00  72.00  86.87   14
 26  \w     62.00  94.00   2.00   35.00    --   90.00  58.00 126.52   16
 27  \w     60.00  90.00   2.00   35.00    --   90.00  68.00 -89.66   15
 28  \w     78.00 106.00   2.00   35.00    --  102.00  54.00 -39.41   14
 29  \w    109.00 157.00   2.00   35.00    --  102.00  77.00-149.68   24
 30  \w     69.00  99.00   2.00   35.00    --  102.00  77.00-149.68   15
 31  \w    114.00 170.00   2.00   35.00    --  106.00  73.00 116.51   28
 32  \w     75.00 101.00   2.00   35.00    --  106.00  73.00 116.51   13
 33  \w    120.00 176.00   2.00   35.00    --  112.00  61.00  90.00   28
 34  \w     85.00 113.00   2.00   35.00    --  112.00  61.00  90.00   14
 35  \w     84.00 146.00   2.00   35.00    --  112.00  61.00   0.00   31
 36  \w     80.00 170.00   2.00   35.00    --  112.00  77.00-120.00   45
 37  \w     50.00 140.00   2.00   35.00    --  112.00 -61.00  90.00   45
 38  \w     37.00 113.00   2.00   35.00    --  112.00-111.00  60.00   38
 39  \w    122.00 166.00   2.00   35.00    --  112.00  61.00 150.00   22
 40  \w     44.00 116.00   2.00   35.00    --  112.00-111.00 -90.00   36
 41  \w     83.00 109.00   2.00   35.00    --  112.00  61.00 150.00   13
 42  \w    129.00 157.00   2.00   35.00    --  112.00  61.00-120.00   14
 43  \w     83.00 113.00   2.00   35.00    --  112.00  61.00-120.00   15
 44  \w     79.00 159.00   2.00   35.00    --  112.00  77.00   0.00   40
 45  \w     79.00 167.00   2.00   35.00    --  112.00  77.00 -90.00   44
 46  \w     79.00 173.00   2.00   35.00    --  112.00  77.00  30.00   47
 47  \w     79.00 165.00   2.00   35.00    --  112.00  77.00-180.00   43
 48  \w     79.00 119.00   2.00   35.00    --  112.00  77.00 150.00   20
 49  \w     55.00 139.00   2.00   35.00    --  112.00 -61.00-120.00   42
 50  \w    130.00 160.00   2.00   35.00    --  112.00  77.00 -30.00   15
 51  \w     83.00 111.00   2.00   35.00    --  112.00  61.00 -30.00   14
 52  \w     79.00 123.00   2.00   35.00    --  112.00  77.00 -30.00   22
 53  \w    116.00 176.00   2.00   35.00    --  112.00  77.00 -60.00   30
 54  \w     79.00 107.00   2.00   35.00    --  112.00  77.00 -60.00   14
 55  \w     84.00 116.00   2.00   35.00    --  112.00-111.00-180.00   16
 56  \w    117.00 171.00   2.00   35.00    --  112.00  77.00  60.00   27
 57  \w     80.00 106.00   2.00   35.00    --  112.00  77.00  60.00   13
 58  \w     29.00 103.00   2.00   35.00    --  112.00 -94.00  90.00   37
;
_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      0.0163712000
_diffrn_orient_matrix_UB_12      0.0052373000
_diffrn_orient_matrix_UB_13      -0.0996948000
_diffrn_orient_matrix_UB_21      -0.2376078000
_diffrn_orient_matrix_UB_22      -0.0282731000
_diffrn_orient_matrix_UB_23      -0.0343006000
_diffrn_orient_matrix_UB_31      -0.0343726000
_diffrn_orient_matrix_UB_32      0.1100837000
_diffrn_orient_matrix_UB_33      0.0391641000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0501
_diffrn_reflns_av_unetI/netI     0.0501
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            28838
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.995
_diffrn_reflns_theta_min         3.638
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.741
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.938
_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    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.114
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 3333 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(11)
_refine_ls_extinction_coef       0.0020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     688
_refine_ls_number_reflns         9722
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0492P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.0963
_reflns_Friedel_coverage         0.903
_reflns_Friedel_fraction_full    0.915
_reflns_Friedel_fraction_max     0.902
_reflns_number_gt                8303
_reflns_number_total             9722
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01113_si_001.cif
_cod_data_source_block           6a
_cod_original_cell_volume        1304.33(16)
_cod_database_code               4032578
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C27 H29 N5 O5'
_reflns_odcompleteness_completeness 99.84
_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
 N11B-H11B = N11A-H11A
 0.85 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C29A(H29A),
 C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C21B(H21B), C22B(H22B),
 C23B(H23B), C24B(H24B), C25B(H25B), C29B(H29B), C30B(H30B), C31B(H31B),
 C32B(H32B), C33B(H33B)
3.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), C37A(H37A,H37B,H37C), C16B(H16D,H16E,H16F),
 C17B(H17D,H17E,H17F), C18B(H18D,H18E,H18F), C26B(H26D,H26E,H26F), C27B(H27D,
 H27E,H27F), C37B(H37D,H37E,H37F)
;
_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 1.147
_oxdiff_exptl_absorpt_empirical_full_min 0.811