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_4518756
_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             2020-11-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2890(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2799(2)
_cell_length_b                   5.20460(10)
_cell_length_c                   12.4362(2)
_cell_measurement_reflns_used    9006
_cell_measurement_temperature    169.99(11)
_cell_measurement_theta_max      74.7900
_cell_measurement_theta_min      3.5440
_cell_volume                     665.20(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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    -73.00  26.00   0.50    0.05    --  -47.20  83.00  82.00  198
  2  \w    -24.00  73.00   0.50    0.05    --   47.20 -83.00 -37.00  194
  3  \w   -168.00 -79.00   0.50    0.50    --  -99.00 -83.00 -37.00  178
  4  \w     31.00 129.00   0.50    0.50    --  103.25 -83.00 -37.00  196
  5  \w     86.00 169.00   0.50    0.50    --  103.25  83.00  82.00  166
  6  \w   -120.00 -74.00   0.50    0.05    --  -47.20-125.00  90.00   92
  7  \w    -23.00  28.00   0.50    0.05    --  -47.20  19.00  60.00  102
  8  \w   -120.00 -32.00   0.50    0.05    --  -47.20 -57.00 -90.00  176
  9  \w    -23.00  28.00   0.50    0.05    --  -47.20  19.00 120.00  102
 10  \w    -26.00  47.00   0.50    0.05    --   47.20 -38.00-120.00  146
 11  \w    -68.00 -26.00   0.50    0.50    --  -99.00  61.00   0.00   84
 12  \w   -168.00 -86.00   0.50    0.50    --  -99.00 -45.00-120.00  164
 13  \w   -168.00 -82.00   0.50    0.50    --  -99.00 -61.00  60.00  172
 14  \w   -112.00 -26.00   0.50    0.50    --  -99.00 125.00-120.00  172
 15  \w   -168.00 -82.00   0.50    0.50    --  -99.00 -61.00 -90.00  172
 16  \w   -168.00 -86.00   0.50    0.50    --  -99.00 -45.00-150.00  164
 17  \w    -68.00 -26.00   0.50    0.50    --  -99.00  61.00 -90.00   84
 18  \w    -68.00 -26.00   0.50    0.50    --  -99.00  61.00 -60.00   84
 19  \w   -124.00 -26.00   0.50    0.50    --  -99.00  83.00  82.00  196
 20  \w    -68.00 -26.00   0.50    0.50    --  -99.00  61.00  30.00   84
 21  \w     31.00  75.00   0.50    0.50    --  103.25 -61.00-120.00   88
 22  \w     91.00 169.00   0.50    0.50    --  103.25  45.00-120.00  156
 23  \w     31.00  75.00   0.50    0.50    --  103.25 -61.00  90.00   88
 24  \w     91.00 169.00   0.50    0.50    --  103.25  45.00 -60.00  156
 25  \w     31.00 106.00   0.50    0.50    --  103.25 -94.00   0.00  150
 26  \w     31.00  75.00   0.50    0.50    --  103.25 -61.00 150.00   88
 27  \w     31.00 111.00   0.50    0.50    --  103.25-125.00 120.00  160
 28  \w     87.00 169.00   0.50    0.50    --  103.25  61.00   0.00  164
 29  \w     91.00 169.00   0.50    0.50    --  103.25  45.00  30.00  156
 30  \w     31.00  75.00   0.50    0.50    --  103.25 -61.00   0.00   88
 31  \w   -120.00 -32.00   0.50    0.05    --  -47.20 -57.00 120.00  176
 32  \w   -120.00 -24.00   0.50    0.05    --  -47.20 -77.00  30.00  192
 33  \w   -120.00 -24.00   0.50    0.05    --  -47.20 -77.00  90.00  192
 34  \w   -120.00 -34.00   0.50    0.05    --  -47.20 -38.00 -60.00  172
 35  \w   -120.00 -32.00   0.50    0.05    --  -47.20 -57.00-150.00  176
 36  \w   -120.00 -32.00   0.50    0.05    --  -47.20 -57.00-180.00  176
 37  \w    -27.00  30.00   0.50    0.05    --   47.20 -19.00 150.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0675127000
_diffrn_orient_matrix_UB_12      -0.2392005000
_diffrn_orient_matrix_UB_13      0.0482483000
_diffrn_orient_matrix_UB_21      0.0262480000
_diffrn_orient_matrix_UB_22      -0.0998361000
_diffrn_orient_matrix_UB_23      -0.1141073000
_diffrn_orient_matrix_UB_31      0.1311710000
_diffrn_orient_matrix_UB_32      0.1432445000
_diffrn_orient_matrix_UB_33      0.0011379000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12599
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.606
_diffrn_reflns_theta_min         3.555
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.799
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent light colourless'
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       needle
_exptl_crystal_F_000             280
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1062 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2644
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0473P)^2^+0.0940P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0815
_refine_ls_wR_factor_ref         0.0823
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.919
_reflns_number_gt                2553
_reflns_number_total             2644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01220_si_003.cif
_cod_data_source_block           tx3757
_cod_database_code               4518756
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'C H N O'
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.567
_reflns_odcompleteness_completeness 100.00
_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,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C3(H3A,H3B), C2(H2A,H2B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C14(H14), C13(H13)
2.d X=CH2 refined with riding coordinates:
 N1(H1A,H1B)
;
_shelx_res_checksum              74034
_shelx_hkl_checksum              6767
_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 1.306
_oxdiff_exptl_absorpt_empirical_full_min 0.811