Reversal and Amplification of the Enantioselectivity of Biocatalytic Desymmetrization toward Meso Heterocyclic Dicarboxamides Enabled by Rational Engineering of Amidase
Ao, Yu-Fei; Hu, Hui-Juan; Zhao, Cheng-Xin; Chen, Peng; Huang, Tingting; Chen, Hui; Wang, Qi-Qiang; Wang, De-Xian; Wang, Mei-Xiang; ACS Catalysis  (2021) 6900–6907; doi:10.1021/acscatal.1c01220

data_4518757
_publ_section_title
;
 Reversal and Amplification of the Enantioselectivity of Biocatalytic
 Desymmetrization toward Meso Heterocyclic Dicarboxamides Enabled by
 Rational Engineering of Amidase
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6900
_journal_page_last               6907
_journal_paper_doi               10.1021/acscatal.1c01220
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H17 N O4'
_chemical_formula_sum            'C14 H17 N O4'
_chemical_formula_weight         263.28
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.829(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9990(2)
_cell_length_b                   14.9431(3)
_cell_length_c                   11.0324(2)
_cell_measurement_reflns_used    20074
_cell_measurement_temperature    170.01(10)
_cell_measurement_theta_max      30.6680
_cell_measurement_theta_min      1.8500
_cell_volume                     1311.88(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.905
_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   -100.00  78.00   0.50    5.00    --  -11.40  45.00 -12.34  356
  2  \w   -100.00  78.00   0.50    5.00    --  -11.40  45.00 120.00  356
  3  \w   -100.00  78.00   0.50    5.00    --  -11.40  45.00  60.00  356
  4  \w   -100.00  78.00   0.50    5.00    --  -11.40  45.00 178.51  356
  5  \w    -84.00  27.00   0.50    5.00    --    5.00  45.00  90.00  222
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0528080000
_diffrn_orient_matrix_UB_12      0.0365523000
_diffrn_orient_matrix_UB_13      0.0192049000
_diffrn_orient_matrix_UB_21      -0.0713701000
_diffrn_orient_matrix_UB_22      0.0282788000
_diffrn_orient_matrix_UB_23      -0.0009765000
_diffrn_orient_matrix_UB_31      -0.0080603000
_diffrn_orient_matrix_UB_32      -0.0108229000
_diffrn_orient_matrix_UB_33      0.0616939000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32333
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.046
_diffrn_reflns_theta_min         1.855
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.098
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65407
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45i (Rigaku Oxford Diffraction, 2018)
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    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 2932 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         7224
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0428P)^2^+0.0935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0763
_refine_ls_wR_factor_ref         0.0779
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.813
_reflns_number_gt                6730
_reflns_number_total             7224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01220_si_002.cif
_cod_data_source_block           mx8954
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C28 H34 N2 O8'
_cod_original_formula_weight         526.57
_cod_original_formula_moiety         '2(C14 H17 N O4)'
_cod_original_formula_units_Z            2
_cod_database_code               4518757
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHON
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.973
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C6(H6), C16(H16), C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C8(H8A,H8B), C17(H17A,H17B), C18(H18A,
 H18B), C19(H19A,H19B), C22(H22A,H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C24(H24), C25(H25),
 C26(H26), C27(H27), C28(H28)
2.d X=CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B)
;
_shelx_res_checksum              60827
_shelx_hkl_checksum              62610
_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 1.716
_oxdiff_exptl_absorpt_empirical_full_min 0.664