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_4135323
_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_formula_moiety         'C17 H15 N O3'
_chemical_formula_sum            'C17 H15 N O3'
_chemical_formula_weight         281.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-06-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.026(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7380(3)
_cell_length_b                   4.40640(10)
_cell_length_c                   27.5661(8)
_cell_measurement_reflns_used    2311
_cell_measurement_temperature    295.4(4)
_cell_measurement_theta_max      70.6330
_cell_measurement_theta_min      4.2030
_cell_volume                     1422.26(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.4(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.965
_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    -83.00 -58.00   1.00    1.60    --  -35.62 -25.00 116.00   25
  2  \w    -61.00  32.00   1.00    1.60    --  -35.62  25.00 -79.00   93
  3  \w     34.00  59.00   1.00    1.60    --   35.62  25.00 -79.00   25
  4  \w    -22.00  37.00   1.00    1.60    --   35.62 -25.00 116.00   59
  5  \w     90.00 156.00   1.00    6.41    --  107.12  25.00 -79.00   66
  6  \w     40.00 109.00   1.00    6.41    --  107.12 -25.00 116.00   69
  7  \w   -107.00 -18.00   1.00    1.60    --  -35.62 -19.00 -90.00   89
  8  \w   -108.00 -55.00   1.00    1.60    --  -35.62-178.00 -90.00   53
  9  \w     64.00  89.00   1.00    1.60    --   35.62 178.00  60.00   25
 10  \w     58.00  97.00   1.00    1.60    --   35.62 178.00 150.00   39
 11  \w     38.00  64.00   1.00    6.41    --  107.12-111.00 -30.00   26
 12  \w     91.00 165.00   1.00    6.41    --  107.12  61.00 -60.00   74
 13  \w    146.00 172.00   1.00    6.41    --  107.12 111.00 150.00   26
 14  \w     62.00 110.00   1.00    6.41    --  107.12 -95.00 -30.00   48
 15  \w     43.00 108.00   1.00    6.41    --  107.12 -30.00 -60.00   65
 16  \w    113.00 139.00   1.00    6.41    --  107.12 111.00 150.00   26
 17  \w     45.00 125.00   1.00    6.41    --  107.12 -61.00-150.00   80
 18  \w     67.00  92.00   1.00    6.41    --  107.12-111.00 -30.00   25
 19  \w     44.00  76.00   1.00    6.41    --  107.12 -95.00 150.00   32
;
_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      0.0129298000
_diffrn_orient_matrix_UB_12      0.1063999000
_diffrn_orient_matrix_UB_13      0.0533491000
_diffrn_orient_matrix_UB_21      0.1296079000
_diffrn_orient_matrix_UB_22      0.0367366000
_diffrn_orient_matrix_UB_23      -0.0037199000
_diffrn_orient_matrix_UB_31      -0.0185590000
_diffrn_orient_matrix_UB_32      0.3310045000
_diffrn_orient_matrix_UB_33      -0.0167036000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -3
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            5343
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.385
_diffrn_reflns_theta_min         3.998
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34770
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (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    1.314
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.270
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.256
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2681
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.256
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0613
_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^)+(0.0426P)^2^+1.7375P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1856
_refine_ls_wR_factor_ref         0.1907
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2201
_reflns_number_total             2681
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09075_si_002.cif
_cod_data_source_block           hb-20200616
_cod_database_code               4135323
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 N1 O1'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.826
_diffrn_oxdiff_digest_frames
;
01a45fe94306f4a4c81735fd9095ec0f8800985ab02
;
_diffrn_oxdiff_digest_hkl
;
01fe1efe8469269cfd3818f0c7a69e60a432b4
;
_reflns_odcompleteness_completeness 99.52
_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:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C18(H18), C5(H5), C14(H14), C3(H3), C17(H17), C15(H15),
 C16(H16)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              33701
_shelx_hkl_checksum              17647
_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 1.949
_oxdiff_exptl_absorpt_empirical_full_min 0.254