Rational Design of 2-Substituted DMAP-<i>N</i>-oxides as Acyl Transfer Catalysts: Dynamic Kinetic Resolution of Azlactones.
Xie, Ming-Sheng; Huang, Bin; Li, Ning; Tian, Yin; Wu, Xiao-Xia; Deng, Yun; Qu, Gui-Rong; Guo, Hai-Ming; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c09075

data_4135325
_publ_section_title
;
 Rational Design of 2-Substituted DMAP-<i>N</i>-oxides as Acyl Transfer
 Catalysts: Dynamic Kinetic Resolution of Azlactones.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c09075
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H28 N4 O4'
_chemical_formula_sum            'C22 H28 N4 O4'
_chemical_formula_weight         412.48
_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     iterative
_audit_creation_date             2019-01-04
_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                   5.49233(5)
_cell_length_b                   12.68068(13)
_cell_length_c                   30.6855(3)
_cell_measurement_reflns_used    16591
_cell_measurement_temperature    290.8(8)
_cell_measurement_theta_max      71.2300
_cell_measurement_theta_min      4.4970
_cell_volume                     2137.14(4)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.8(8)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_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    -52.00  32.00   1.00    1.80    --  -35.37  57.00-120.00   84
  2  \w      1.00  74.00   1.00    1.80    --   35.37 -99.00  60.00   73
  3  \w    -34.00  54.00   1.00    1.80    --   35.37 -38.00 120.00   88
  4  \w     19.00 103.00   1.00    1.80    --   35.37  57.00  90.00   84
  5  \w    100.00 176.00   1.00    9.00    --  106.50 111.00   0.00   76
  6  \w     57.00 151.00   1.00    9.00    --  106.50 178.00 150.00   94
  7  \w     88.00 173.00   1.00    9.00    --  106.50  61.00 120.00   85
  8  \w     85.00 176.00   1.00    9.00    --  106.50  30.00-120.00   91
  9  \w     37.00 109.00   1.00    9.00    --  106.50 -95.00-150.00   72
 10  \w     40.00 125.00   1.00    9.00    --  106.50 -61.00 -30.00   85
 11  \w     40.00 125.00   1.00    9.00    --  106.50 -61.00  60.00   85
 12  \w    -54.00  34.00   1.00    1.80    --  -35.37  38.00   0.00   88
 13  \w     19.00 103.00   1.00    1.80    --   35.37  57.00  30.00   84
 14  \w     19.00 103.00   1.00    1.80    --   35.37  57.00-150.00   84
 15  \w      9.00 103.00   1.00    1.80    --   35.37  77.00 -90.00   94
 16  \w     37.00 112.00   1.00    9.00    --  106.50-111.00 120.00   75
 17  \w     89.00 175.00   1.00    9.00    --  106.50  45.00-180.00   86
 18  \w     68.00 178.00   1.00    9.00    --  106.50  15.00   0.00  110
 19  \w     89.00 175.00   1.00    9.00    --  106.50  45.00  30.00   86
 20  \w     80.00 174.00   1.00    9.00    --  106.50  77.00  60.00   94
 21  \w     80.00 174.00   1.00    9.00    --  106.50  77.00  90.00   94
 22  \w     37.00 109.00   1.00    9.00    --  106.50 -95.00 -30.00   72
 23  \w     88.00 173.00   1.00    9.00    --  106.50  61.00 -90.00   85
 24  \w    -32.00  52.00   1.00    1.80    --   35.37 -57.00  60.00   84
 25  \w     19.00 103.00   1.00    1.80    --   35.37  57.00-120.00   84
 26  \w     19.00 103.00   1.00    1.80    --   35.37  57.00 150.00   84
 27  \w     23.00  89.00   1.00    1.80    --   35.37-125.00 -60.00   66
 28  \w     80.00 174.00   1.00    9.00    --  106.50  77.00-150.00   94
 29  \w     89.00 175.00   1.00    9.00    --  106.50  45.00 150.00   86
 30  \w     80.00 174.00   1.00    9.00    --  106.50  77.00  30.00   94
 31  \w     80.00 174.00   1.00    9.00    --  106.50  77.00-180.00   94
 32  \w     80.00 174.00   1.00    9.00    --  106.50  77.00 -30.00   94
 33  \w     88.00 173.00   1.00    9.00    --  106.50  61.00   0.00   85
 34  \w     80.00 174.00   1.00    9.00    --  106.50  77.00 -60.00   94
 35  \w     88.00 173.00   1.00    9.00    --  106.50  61.00-120.00   85
 36  \w      9.00 103.00   1.00    1.80    --   35.37  77.00 -30.00   94
 37  \w      9.00 103.00   1.00    1.80    --   35.37  77.00  90.00   94
 38  \w      9.00 103.00   1.00    1.80    --   35.37  77.00-150.00   94
 39  \w     23.00  89.00   1.00    1.80    --   35.37-125.00-180.00   66
 40  \w     88.00 173.00   1.00    9.00    --  106.50  61.00 150.00   85
 41  \w     80.00 174.00   1.00    9.00    --  106.50  77.00-101.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2260419000
_diffrn_orient_matrix_UB_12      0.0588367000
_diffrn_orient_matrix_UB_13      -0.0171250000
_diffrn_orient_matrix_UB_21      0.0630253000
_diffrn_orient_matrix_UB_22      0.0343374000
_diffrn_orient_matrix_UB_23      0.0468266000
_diffrn_orient_matrix_UB_31      0.1536753000
_diffrn_orient_matrix_UB_32      -0.1005537000
_diffrn_orient_matrix_UB_33      0.0059687000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            35807
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.313
_diffrn_reflns_theta_min         3.772
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72707
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.250
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1593 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         4141
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0739P)^2^+0.1640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.705
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                4006
_reflns_number_total             4141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09075_si_003.cif
_cod_data_source_block           ln-20190102
_cod_database_code               4135325
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.898
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C28(H28), C11(H11), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 N14(H14), C5(H5), C23(H23), C2(H2), C22(H22), C3(H3), C21(H21)
2.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C29(H29A,H29B,H29C), C27(H27A,H27B,H27C), C26(H26A,H26B,
 H26C)
;
_shelx_res_checksum              70744
_shelx_hkl_checksum              29164
_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 1.778
_oxdiff_exptl_absorpt_empirical_full_min 0.585