Organocatalytic Asymmetric Michael Addition of Pyrazol-5-ones to β-Trifluoromethyl-α,β-unsaturated ketones: Stereocontrolled Construction of Vicinal Quaternary and Tertiary Stereocenters.
Xu, Xinyao; He, Yanmin; Zhou, Jingqi; Li, Xinjuan; Zhu, Bo; Chang, Junbiao; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02676

data_4037709
_publ_section_title
;
 Organocatalytic Asymmetric Michael Addition of Pyrazol-5-ones to
 \b-Trifluoromethyl-\a,\b-unsaturated ketones: Stereocontrolled
 Construction of Vicinal Quaternary and Tertiary Stereocenters.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02676
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H20 Br F3 N2 O'
_chemical_formula_sum            'C26 H20 Br F3 N2 O'
_chemical_formula_weight         513.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5490(2)
_cell_length_b                   15.9048(2)
_cell_length_c                   7.70900(10)
_cell_measurement_reflns_used    18604
_cell_measurement_temperature    295(3)
_cell_measurement_theta_max      72.1060
_cell_measurement_theta_min      4.7480
_cell_volume                     2274.29(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_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_environment      air
_diffrn_ambient_temperature      295(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_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   -115.00 -16.00   1.00    1.00    --  -40.77 -38.00 121.00   99
  2  \w     97.00 178.00   1.00    3.83    --  103.55  83.00  70.00   81
  3  \w     29.00 128.00   1.00    3.83    --  103.55 -38.00 121.00   99
  4  \w     93.00 176.00   1.00    3.83    --  103.55 127.00 140.00   83
  5  \w     83.00 176.00   1.00    3.83    --  103.55 144.00 -50.00   93
  6  \w    -92.00  -2.00   1.00    1.00    --  -40.77 125.00  60.00   90
  7  \w     16.00 115.00   1.00    1.00    --   40.77  38.00-180.00   99
  8  \w     57.00 150.00   1.00    3.83    --  103.55 178.00-120.00   93
  9  \w    100.00 178.00   1.00    3.83    --  103.55 111.00-180.00   78
 10  \w    100.00 178.00   1.00    3.83    --  103.55 111.00  90.00   78
 11  \w    100.00 178.00   1.00    3.83    --  103.55 111.00  30.00   78
 12  \w    -65.00  34.00   1.00    1.00    --  -40.77  38.00 -60.00   99
 13  \w   -113.00 -13.00   1.00    1.00    --  -40.77 -57.00-120.00  100
 14  \w   -113.00 -13.00   1.00    1.00    --  -40.77 -57.00   0.00  100
 15  \w     51.00 178.00   1.00    3.83    --  103.55  15.00  30.00  127
 16  \w     74.00 176.00   1.00    3.83    --  103.55  61.00 150.00  102
 17  \w     74.00 176.00   1.00    3.83    --  103.55  61.00-150.00  102
 18  \w     71.00 178.00   1.00    3.83    --  103.55  77.00  90.00  107
 19  \w     74.00 176.00   1.00    3.83    --  103.55  61.00  60.00  102
 20  \w     75.00 178.00   1.00    3.83    --  103.55  30.00 -90.00  103
 21  \w   -117.00  -8.00   1.00    1.00    --  -40.77 -77.00 120.00  109
 22  \w   -113.00 -61.00   1.00    1.00    --  -40.77-144.00-104.00   52
 23  \w      8.00 117.00   1.00    1.00    --   40.77  77.00 -30.00  109
 24  \w     71.00 178.00   1.00    3.83    --  103.55  77.00-120.00  107
 25  \w     71.00 178.00   1.00    3.83    --  103.55  77.00   0.00  107
 26  \w     74.00 176.00   1.00    3.83    --  103.55  61.00-180.00  102
 27  \w     27.00 112.00   1.00    3.83    --  103.55-111.00 -90.00   85
 28  \w     71.00 178.00   1.00    3.83    --  103.55  77.00 -30.00  107
 29  \w     71.00 178.00   1.00    3.83    --  103.55  77.00 -90.00  107
 30  \w   -117.00  -8.00   1.00    1.00    --  -40.77 -77.00-150.00  109
 31  \w      8.00 117.00   1.00    1.00    --   40.77  77.00  60.00  109
 32  \w     23.00  97.00   1.00    1.00    --   40.77-125.00 -90.00   74
 33  \w     74.00 120.00   1.00    3.83    --  103.55  61.00  30.00   46
 34  \w     74.00 176.00   1.00    3.83    --  103.55  61.00 120.00  102
 35  \w     71.00 178.00   1.00    3.83    --  103.55  77.00 -60.00  107
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0382203000
_diffrn_orient_matrix_UB_12      -0.0183803000
_diffrn_orient_matrix_UB_13      0.1732821000
_diffrn_orient_matrix_UB_21      -0.0144219000
_diffrn_orient_matrix_UB_22      0.0946555000
_diffrn_orient_matrix_UB_23      0.0243703000
_diffrn_orient_matrix_UB_31      -0.0723270000
_diffrn_orient_matrix_UB_32      -0.0091423000
_diffrn_orient_matrix_UB_33      -0.0964737000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            46803
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.433
_diffrn_reflns_theta_min         3.661
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.866
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1677 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.041(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4501
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0286
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0399P)^2^+0.5194P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0731
_refine_ls_wR_factor_ref         0.0761
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4178
_reflns_number_total             4501
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02676_si_003.cif
_cod_data_source_block           xxy-20190531
_cod_database_code               4037709
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1 F1 Br1 S1'
_shelx_estimated_absorpt_t_max   0.626
_shelx_estimated_absorpt_t_min   0.534
_diffrn_oxdiff_digest_frames
;
013edf2f28240abf3ce43aa607e11ba5a400032bcd9
;
_diffrn_oxdiff_digest_hkl
;
01b35f9e1b2c62e9b355d748cec3f0147cd174
;
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C20(H20), C16(H16), C3(H3), C19(H19), C2(H2), C18(H18),
 C31(H31), C6(H6), C17(H17), C27(H27), C30(H30), C5(H5), C29(H29), C28(H28)
2.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              84290
_shelx_hkl_checksum              65799
_olex2_date_sample_data_collection 2019-06-03
_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 1.529
_oxdiff_exptl_absorpt_empirical_full_min 0.678