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_4037710
_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 F4 N2 O2'
_chemical_formula_sum            'C26 H20 F4 N2 O2'
_chemical_formula_weight         468.44
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-28
_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            8
_cell_length_a                   10.67970(10)
_cell_length_b                   14.61600(10)
_cell_length_c                   28.3819(2)
_cell_measurement_reflns_used    42410
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.3960
_cell_measurement_theta_min      4.1230
_cell_volume                     4430.26(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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     19.00  94.00   1.00    1.00    --   40.77-120.00 142.00   75
  2  \w     75.00 178.00   1.00    1.00    --  103.55  30.00 158.00  103
  3  \w     29.00 113.00   1.00    1.00    --  103.55-120.00 142.00   84
  4  \w     21.00 109.00   1.00    1.00    --  103.55 -94.00-138.00   88
  5  \w    -65.00  34.00   1.00    1.00    --  -40.77  38.00 -60.00   99
  6  \w    -65.00  34.00   1.00    1.00    --  -40.77  38.00 120.00   99
  7  \w    -65.00  34.00   1.00    1.00    --  -40.77  38.00-150.00   99
  8  \w     78.00 177.00   1.00    1.00    --  103.55  45.00-150.00   99
  9  \w    100.00 178.00   1.00    1.00    --  103.55 111.00  30.00   78
 10  \w    100.00 178.00   1.00    1.00    --  103.55 111.00-120.00   78
 11  \w     27.00 136.00   1.00    1.00    --  103.55 -77.00 -60.00  109
 12  \w     13.00 113.00   1.00    1.00    --   40.77  57.00  60.00  100
 13  \w     13.00 113.00   1.00    1.00    --   40.77  57.00 -30.00  100
 14  \w      8.00 117.00   1.00    1.00    --   40.77  77.00 150.00  109
 15  \w     74.00 176.00   1.00    1.00    --  103.55  61.00 -90.00  102
 16  \w     78.00 177.00   1.00    1.00    --  103.55  45.00  60.00   99
 17  \w     71.00 178.00   1.00    1.00    --  103.55  77.00   0.00  107
 18  \w     71.00 178.00   1.00    1.00    --  103.55  77.00 150.00  107
 19  \w     74.00 176.00   1.00    1.00    --  103.55  61.00  90.00  102
 20  \w     78.00 177.00   1.00    1.00    --  103.55  45.00 -30.00   99
 21  \w    -65.00  34.00   1.00    1.00    --  -40.77  38.00  30.00   99
 22  \w      8.00 117.00   1.00    1.00    --   40.77  77.00  60.00  109
 23  \w      8.00 117.00   1.00    1.00    --   40.77  77.00-120.00  109
 24  \w     71.00 178.00   1.00    1.00    --  103.55  77.00 120.00  107
 25  \w     74.00 176.00   1.00    1.00    --  103.55  61.00-120.00  102
 26  \w     71.00 178.00   1.00    1.00    --  103.55  77.00 -30.00  107
 27  \w     74.00 176.00   1.00    1.00    --  103.55  61.00-150.00  102
 28  \w     71.00 178.00   1.00    1.00    --  103.55  77.00 -90.00  107
 29  \w    100.00 178.00   1.00    1.00    --  103.55 111.00 -60.00   78
 30  \w   -115.00 -16.00   1.00    1.00    --  -40.77 -38.00 -90.00   99
 31  \w   -121.00   0.00   1.00    1.00    --  -40.77 -19.00 -30.00  121
 32  \w      8.00 117.00   1.00    1.00    --   40.77  77.00 -30.00  109
 33  \w     71.00 178.00   1.00    1.00    --  103.55  77.00  90.00  107
 34  \w     74.00 176.00   1.00    1.00    --  103.55  61.00  60.00  102
;
_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      0.0157226000
_diffrn_orient_matrix_UB_12      0.0081069000
_diffrn_orient_matrix_UB_13      0.0537981000
_diffrn_orient_matrix_UB_21      -0.1330805000
_diffrn_orient_matrix_UB_22      0.0399837000
_diffrn_orient_matrix_UB_23      0.0038950000
_diffrn_orient_matrix_UB_31      -0.0533971000
_diffrn_orient_matrix_UB_32      -0.0971861000
_diffrn_orient_matrix_UB_33      0.0060756000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            91435
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.487
_diffrn_reflns_theta_min         4.342
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.956
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70509
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.405
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.622
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 3586 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         8727
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0762P)^2^+1.5813P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1195
_refine_ls_wR_factor_ref         0.1214
_reflns_Friedel_coverage         0.787
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                8388
_reflns_number_total             8727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02676_si_002.cif
_cod_data_source_block           xxr-20190306
_cod_depositor_comments
;

2020-08-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C26 H20 F4 N2 O2)'
_cod_original_formula_sum        'C52 H40 F8 N4 O4'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     936.88
_cod_database_code               4037710
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 F1'
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.796
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00Z(H00Z), C01G(H01N)
2.b Secondary CH2 refined with riding coordinates:
 C012(H01A,H01B), C01L(H01Q,H01S)
2.c Aromatic/amide H refined with riding coordinates:
 C00M(H00M), C00O(H00O), C00R(H00R), C00V(H00V), C00W(H00W), C00X(H00X),
 C010(H010), C013(H013), C016(H016), C019(H019), C01A(H01J), C01C(H01F),
 C01D(H01G), C01F(H01H), C01I(H01I), C01J(H01O), C01K(H01P), C01M(H01T),
 C01N(H01X), C01O(H01Y), C01P(H01Z), C01Q(H01), C01R(H01R), C01S(H0AA),
 C01T(H1AA), C01U(H01U), C01V(H01V), C01W(H01W)
2.d Idealised Me refined as rotating group:
 C015(H01C,H01D,H01E), C01B(H01K,H01L,H01M)
;
_shelx_res_checksum              74651
_shelx_hkl_checksum              63506
_olex2_date_sample_data_collection 2019-03-06
_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 1.247
_oxdiff_exptl_absorpt_empirical_full_min 0.711