A Bifunctional N-Heterocyclic Carbene as a Noncovalent Organocatalyst for Enantioselective Aza-Michael Addition Reactions
Guo, Fangfang; Chen, Jiean; Huang, Yong; ACS Catalysis 11 (2021) 6316–6324; doi:10.1021/acscatal.1c01908

data_4518698
_publ_section_title
;
 A Bifunctional N-Heterocyclic Carbene as a Noncovalent Organocatalyst for
 Enantioselective Aza-Michael Addition Reactions
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              6316
_journal_page_last               6324
_journal_paper_doi               10.1021/acscatal.1c01908
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C24 H24 F6 N5 S, 0.5(H2 O)'
_chemical_formula_sum            'C24 H25 Cl F6 N5 O0.5 S'
_chemical_formula_weight         573.00
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-03
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.932(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.3627(4)
_cell_length_b                   7.45954(17)
_cell_length_c                   20.2256(5)
_cell_measurement_reflns_used    10910
_cell_measurement_temperature    100.00(12)
_cell_measurement_theta_max      73.5030
_cell_measurement_theta_min      2.4990
_cell_volume                     2616.15(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.976
_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    -58.00  14.00   1.00    1.00    --  -40.98  37.00  60.00   72
  2  \w    -78.00  28.00   1.00    1.00    --  -40.98  19.00 -60.00  106
  3  \w    -81.00  20.00   1.00    1.00    --  -40.98  98.00 105.00  101
  4  \w     30.00  69.00   1.00    1.00    --   40.98 -99.00 -60.00   39
  5  \w    -46.00   9.00   1.00    1.00    --   40.98   0.00 -90.00   55
  6  \w     56.00 129.00   1.00    1.00    --   40.98   0.00 -90.00   73
  7  \w     49.00 133.00   1.00    1.00    --  106.95 -61.00   0.00   84
  8  \w     31.00 152.00   1.00    1.00    --  106.95 -15.00-150.00  121
  9  \w     37.00 153.00   1.00    1.00    --  106.95 -15.00 -30.00  116
 10  \w     38.00  65.00   1.00    1.00    --  106.95-124.00-180.00   27
 11  \w     75.00 118.00   1.00    1.00    --  106.95-124.00-180.00   43
 12  \w     98.00 138.00   1.00    1.00    --  106.95  45.00-150.00   40
 13  \w    133.00 177.00   1.00    1.00    --  106.95  45.00  30.00   44
 14  \w     82.00 117.00   1.00    1.00    --  106.95-124.00 -30.00   35
 15  \w     81.00 125.00   1.00    1.00    --  106.95  45.00  30.00   44
 16  \w     77.00 104.00   1.00    1.00    --  106.95 -94.00  30.00   27
 17  \w     27.00  57.00   1.00    1.00    --  106.95 -94.00  30.00   30
 18  \w     36.00 136.00   1.00    1.00    --  106.95 -77.00 150.00  100
 19  \w     27.00  70.00   1.00    2.50    --  106.95 -98.00  -1.00   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0143234000
_diffrn_orient_matrix_UB_12      0.1197743000
_diffrn_orient_matrix_UB_13      0.0614087000
_diffrn_orient_matrix_UB_21      -0.0448172000
_diffrn_orient_matrix_UB_22      0.1536279000
_diffrn_orient_matrix_UB_23      -0.0353791000
_diffrn_orient_matrix_UB_31      -0.0753509000
_diffrn_orient_matrix_UB_32      -0.0686594000
_diffrn_orient_matrix_UB_33      0.0281751000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18088
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.859
_diffrn_reflns_theta_min         2.187
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.659
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44625
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 3466 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.077(12)
_refine_ls_extinction_coef       0.0007(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     691
_refine_ls_number_reflns         10021
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0591
_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^)+(0.1041P)^2^+0.6889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1607
_refine_ls_wR_factor_ref         0.1681
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.904
_reflns_number_gt                9153
_reflns_number_total             10021
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01908_si_002.cif
_cod_data_source_block           gff-2
_cod_depositor_comments
'Adding full bibliography for 4518697--4518698.cif.'
_cod_original_cell_volume        2616.14(11)
_cod_original_formula_sum        'C24 H25 Cl F6 N5 O0.50 S'
_cod_database_code               4518698
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.58
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C35(H35)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C33(H33A,H33B), C34(H34A,H34B),
 C36(H36A,H36B)
2.c Aromatic/amide H refined with riding coordinates:
 N4(H4), N5(H5), N9(H9), N10(H10), C3(H3), C5(H5A), C7(H7), C15(H15), C17(H17),
  C19(H19), C27(H27), C29(H29), C31(H31), C39(H39), C41(H41), C43(H43)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              97993
_shelx_hkl_checksum              12490
_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 2.173
_oxdiff_exptl_absorpt_empirical_full_min 0.426