Enantioselective 1,4-Michael addition reaction of pyrazolin-5-one derivatives with 2-enoylpyridines catalyzed by Cinchona derived squaramides.
Sharma, Vivek; Kaur, Anmolpreet; Sahoo, Subash Chandra; Chimni, Swapandeep Singh; Organic & biomolecular chemistry 16 (2018) 6470–6478; doi:10.1039/c8ob01588k

data_7156376
_publ_section_title
;
 Enantioselective 1,4-Michael addition reaction of pyrazolin-5-one
 derivatives with 2-enoylpyridines catalyzed by Cinchona derived
 squaramides.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6470
_journal_page_last               6478
_journal_paper_doi               10.1039/c8ob01588k
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration syn
_chemical_compound_source        synthesized
_chemical_formula_moiety         'C31 H26 N4 O6 S'
_chemical_formula_sum            'C31 H26 N4 O6 S'
_chemical_formula_weight         582.62
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-28
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2018-06-28 deposited with the CCDC.
2018-08-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.002(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.5644(2)
_cell_length_b                   19.5682(6)
_cell_length_c                   9.8133(3)
_cell_measurement_reflns_used    9227
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.2480
_cell_measurement_theta_min      3.4710
_cell_volume                     1403.07(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.941
_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    -39.00 -14.00   0.50   12.00    --   -9.95 -79.00  15.00   50
  2  \w     20.00  45.00   0.50   12.00    --   -9.95  79.00 139.00   50
  3  \w    -10.00  36.00   0.50   12.00    --   10.22  79.00 139.00   92
  4  \w     -4.00  21.00   0.50   12.00    --   10.22 -79.00  15.00   50
  5  \w    -74.00  13.00   0.50   12.00    --   -9.95 -77.00-180.00  174
  6  \w    -73.00   8.00   0.50   12.00    --   -9.95 -57.00 -30.00  162
  7  \w     13.00  74.00   0.50   12.00    --   10.22  38.00 -90.00  122
  8  \w     -3.00  71.00   0.50   12.00    --   10.22  38.00 150.00  148
  9  \w     29.00  59.00   0.50   12.00    --   10.22-125.00   0.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0735152000
_diffrn_orient_matrix_UB_12      0.0065955000
_diffrn_orient_matrix_UB_13      0.0600533000
_diffrn_orient_matrix_UB_21      -0.0446042000
_diffrn_orient_matrix_UB_22      0.0301226000
_diffrn_orient_matrix_UB_23      0.0138376000
_diffrn_orient_matrix_UB_31      -0.0449096000
_diffrn_orient_matrix_UB_32      -0.0190740000
_diffrn_orient_matrix_UB_33      0.0425328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0198
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            11881
_diffrn_reflns_point_group_measured_fraction_full 0.877
_diffrn_reflns_point_group_measured_fraction_max 0.802
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.365
_diffrn_reflns_theta_min         3.480
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.168
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83879
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetonitrile'
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.107
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1631 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         5108
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0331
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0473P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.657
_reflns_Friedel_fraction_full    0.749
_reflns_Friedel_fraction_max     0.655
_reflns_number_gt                4471
_reflns_number_total             5108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01588k2.cif
_cod_data_source_block           s-1
_cod_depositor_comments          'Adding full bibliography for 7156376.cif.'
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               7156376
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H O S N'
_diffrn_oxdiff_ac3_digest_frames
;
017074e095b922aaedd60a5fbae4e0296a0002551bf
;
_diffrn_oxdiff_ac3_digest_hkl
;
010dd40d9c965c77670c734e7a26d0cfbb9aa0
;
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C29(H29), C28(H28), C11(H11), C21(H21), C10(H10), C31(H31), C8(H8),
 C20(H20), C7(H7), C24(H24), C30(H30), C23(H23), C18(H18), C17(H17), C16(H16),
 C15(H15)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C25(H25A,H25B,H25C)
;
_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 1.402
_oxdiff_exptl_absorpt_empirical_full_min 0.737