Suppression of rapid deactivation of catalytic tetrapeptides in the asymmetric Michael addition of aldehydes to nitroolefins by supporting them on polymers.
Yuan, Meng; Liu, Yang-Xin; Ding, Tie-Ying; Zhang, Ze-Xuan; Lian, Tian-Rui; Zhao, Peng-Fei; Du, Zhi-Hong; Da, Chao-Shan; Organic & biomolecular chemistry 23 (2025) 6819–6831; doi:10.1039/d5ob00667h

data_7160604
_publ_section_title
;
 Suppression of rapid deactivation of catalytic tetrapeptides in the
 asymmetric Michael addition of aldehydes to nitroolefins by supporting
 them on polymers.
;
_journal_issue                   28
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6819
_journal_page_last               6831
_journal_paper_doi               10.1039/d5ob00667h
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C21 H30 N2 O2'
_chemical_formula_sum            'C21 H30 N2 O2'
_chemical_formula_weight         342.47
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-06
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-01-31 deposited with the CCDC.	2025-06-24 downloaded from the CCDC.
;
_cell_angle_alpha                73.689(2)
_cell_angle_beta                 78.406(3)
_cell_angle_gamma                84.583(2)
_cell_formula_units_Z            2
_cell_length_a                   7.8751(2)
_cell_length_b                   9.2837(2)
_cell_length_c                   14.3774(4)
_cell_measurement_reflns_used    14221
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.9330
_cell_measurement_theta_min      3.2320
_cell_volume                     987.44(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.938
_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  88.00   0.50    0.05    --   45.17-153.00 162.00   60
  2  \w     40.00 131.00   0.50    0.06    --  109.64-153.00 162.00  182
  3  \w     47.00 111.00   0.50    0.06    --  109.64-125.00   0.00  128
  4  \w     41.00 109.00   0.50    0.06    --  109.64-121.00 -38.00  136
  5  \w     51.00 104.00   0.50    0.06    --  109.64-125.00-120.00  106
  6  \w     17.00  53.00   0.50    0.05    --   45.17-121.00 -38.00   72
  7  \w     67.00  93.00   0.50    0.06    --  109.64 -94.00 150.00   52
  8  \w     36.00  68.00   0.50    0.06    --  109.64 -61.00 150.00   64
  9  \w     40.00  70.00   0.50    0.06    --  109.64 -77.00 120.00   60
 10  \w     36.00  63.00   0.50    0.06    --  109.64 -61.00 120.00   54
 11  \w     44.00  70.00   0.50    0.06    --  109.64 -77.00 -60.00   52
 12  \w     77.00 103.00   0.50    0.06    --  109.64 -77.00 -60.00   52
 13  \w     43.00  68.00   0.50    0.06    --  109.64 -61.00-150.00   50
 14  \w     71.00  97.00   0.50    0.05    --   45.17 153.00-156.00   52
 15  \w    -15.00  16.00   0.50    0.05    --   20.00  95.00 175.15   62
 16  \w    120.00 145.00   0.50    0.06    --  109.64 121.00  44.00   50
 17  \w     86.00 111.00   0.50    0.06    --  109.64 153.00-156.00   50
 18  \w     98.00 124.00   0.50    0.05    --   56.00  78.00 -16.23   52
 19  \w     70.00  95.00   0.50    0.05    --   56.00  76.00-132.58   50
 20  \w     32.00  59.00   0.50    0.05    --   56.00  78.00 -16.23   54
 21  \w     31.00  57.00   0.50    0.05    --   56.00  76.00-132.58   52
 22  \w     43.00  69.00   0.50    0.05    --   68.00  78.00  38.89   52
 23  \w     45.00  71.00   0.50    0.05    --   68.00  76.00  98.17   52
 24  \w     33.00  59.00   0.50    0.05    --   60.00  78.00 141.76   52
 25  \w     37.00  69.00   0.50    0.05    --   64.00  78.00 172.84   64
 26  \w     36.00  64.00   0.50    0.05    --   60.00  74.00  84.36   56
 27  \w     38.00  66.00   0.50    0.05    --   64.00  74.00  27.03   56
 28  \w     34.00  59.00   0.50    0.05    --   56.00  75.00 -43.18   50
 29  \w     37.00  63.00   0.50    0.05    --   60.00  74.00 -71.28   52
 30  \w     49.00  75.00   0.50    0.05    --   72.00  75.00-130.07   52
 31  \w    105.00 130.00   0.50    0.05    --   56.00  76.00-132.58   50
 32  \w     28.00  64.00   0.50    0.05    --   45.17  37.00 -60.00   72
 33  \w     18.00  47.00   0.50    0.05    --   45.17  77.00 -90.00   58
 34  \w     80.00 105.00   0.50    0.05    --   45.17  77.00 -90.00   50
 35  \w     19.00  44.00   0.50    0.05    --   45.17  77.00  30.00   50
 36  \w     19.00  45.00   0.50    0.05    --   45.17  77.00 150.00   52
 37  \w     57.00  84.00   0.50    0.05    --   45.17  77.00 150.00   54
 38  \w     64.00  90.00   0.50    0.05    --   45.17  37.00  90.00   52
 39  \w     27.00  61.00   0.50    0.05    --   45.17  37.00  90.00   68
 40  \w    -39.00 -13.00   0.50    0.05    --  -44.00 -87.00-177.96   52
 41  \w    -40.00 -14.00   0.50    0.05    --  -44.00 -88.00 -74.97   52
 42  \w    -41.00 -16.00   0.50    0.05    --  -48.00 -90.00  28.74   50
 43  \w    -41.00 -16.00   0.50    0.05    --  -48.00 -89.00  67.75   50
 44  \w   -116.00 -79.00   0.50    0.05    --  -45.17-153.00 162.00   74
 45  \w    -70.00 -44.00   0.50    0.05    --  -72.00 -78.00  99.39   52
 46  \w    -70.00 -45.00   0.50    0.05    --  -72.00 -77.00 -77.52   50
 47  \w    -86.00 -61.00   0.50    0.06    --  -88.00 -77.00-117.81   50
 48  \w   -100.00 -71.00   0.50    0.06    --  -96.00 -77.00-106.49   58
 49  \w   -105.00 -65.00   0.50    0.06    --  -92.00 -77.00-160.73   80
 50  \w   -165.00-116.00   0.50    0.06    --  -92.00 -77.00-160.73   98
 51  \w   -168.00-107.00   0.50    0.06    --  -96.00 -77.00-106.49  122
 52  \w   -157.00 -73.00   0.50    0.06    -- -100.00 -76.00-143.01  168
 53  \w   -107.00 -73.00   0.50    0.06    -- -100.00 -77.00 -60.00   68
 54  \w    -68.00 -37.00   0.50    0.05    --  -64.00 -76.00-172.87   62
 55  \w   -103.00 -75.00   0.50    0.06    -- -100.00 -76.00 -17.68   56
 56  \w   -164.00 -73.00   0.50    0.06    -- -100.00 -77.00  60.00  182
 57  \w   -141.00 -73.00   0.50    0.06    -- -100.00 -77.00 120.00  136
 58  \w    -99.00 -70.00   0.50    0.06    --  -96.00 -74.00 173.70   58
 59  \w    -92.00 -66.00   0.50    0.06    --  -92.00 -75.00 157.75   52
 60  \w    -83.00 -57.00   0.50    0.06    --  -84.00 -76.00 127.61   52
 61  \w    -79.00 -53.00   0.50    0.06    --  -80.00 -76.00  69.80   52
 62  \w    -88.00 -62.00   0.50    0.06    --  -88.00 -74.00  16.61   52
 63  \w    -84.00 -58.00   0.50    0.06    --  -84.00 -74.00  18.34   52
 64  \w    -81.00 -46.00   0.50    0.05    --  -72.00 -74.00 127.32   70
 65  \w    -87.00 -58.00   0.50    0.06    --  -84.00 -74.00 -32.63   58
 66  \w    -97.00 -50.00   0.50    0.05    --  -76.00 -75.00-169.48   94
 67  \w   -112.00 -74.00   0.50    0.06    -- -100.00 -74.00-131.14   76
 68  \w   -171.00-122.00   0.50    0.06    -- -100.00 -74.00-131.14   98
 69  \w   -173.00 -76.00   0.50    0.06    -- -100.00 -73.00 -31.08  194
 70  \w    -89.00 -63.00   0.50    0.06    --  -88.00 -72.00-118.89   52
 71  \w    -77.00 -51.00   0.50    0.05    --  -76.00 -73.00 -96.02   52
 72  \w    -80.00 -55.00   0.50    0.06    --  -80.00 -71.00-157.10   50
 73  \w    -90.00 -56.00   0.50    0.06    --  -80.00 -72.00 -51.88   68
 74  \w    -91.00 -59.00   0.50    0.06    --  -84.00 -71.00  -3.54   64
 75  \w    -88.00 -63.00   0.50    0.06    --  -88.00 -72.00  42.25   50
 76  \w    -86.00 -60.00   0.50    0.06    --  -84.00 -73.00  59.57   52
 77  \w   -157.00 -97.00   0.50    0.06    --  -84.00 -71.00  -3.54  120
 78  \w   -159.00-128.00   0.50    0.06    -- -100.00 -71.00  76.65   62
 79  \w   -123.00 -83.00   0.50    0.06    -- -100.00 -71.00  76.65   80
 80  \w   -139.00 -67.00   0.50    0.06    --  -92.00 -71.00 122.47  144
 81  \w   -158.00-109.00   0.50    0.06    --  -96.00 -74.00 173.70   98
 82  \w    -80.00 -44.00   0.50    0.05    --  -68.00 -70.00 137.38   72
 83  \w    -69.00 -43.00   0.50    0.05    --  -68.00 -71.00  33.04   52
 84  \w   -107.00 -76.00   0.50    0.06    -- -100.00 -69.00  39.57   62
 85  \w   -149.00-121.00   0.50    0.06    -- -100.00 -69.00  39.57   56
 86  \w   -151.00 -79.00   0.50    0.06    -- -100.00 -67.00   3.94  144
 87  \w   -101.00 -76.00   0.50    0.06    -- -100.00 -69.00 -50.42   50
 88  \w    -78.00 -42.00   0.50    0.05    --  -64.00 -67.00 -56.39   72
 89  \w    -72.00 -40.00   0.50    0.05    --  -64.00 -70.00-152.96   64
 90  \w    -88.00 -62.00   0.50    0.06    --  -84.00 -66.00-120.77   52
 91  \w    -90.00 -57.00   0.50    0.06    --  -80.00 -66.00 -78.48   66
 92  \w   -136.00-109.00   0.50    0.06    --  -80.00 -66.00 -78.48   54
 93  \w   -166.00 -77.00   0.50    0.06    -- -100.00 -66.00 -10.38  178
 94  \w   -162.00 -70.00   0.50    0.06    --  -92.00 -65.00  88.49  184
 95  \w   -168.00 -79.00   0.50    0.06    -- -100.00 -67.00 146.89  178
 96  \w   -107.00 -70.00   0.50    0.06    --  -92.00 -65.00 171.27   74
 97  \w    -99.00 -63.00   0.50    0.06    --  -84.00 -62.00 122.15   72
 98  \w    -66.00 -27.00   0.50    0.05    --  -45.17 -57.00  60.00   78
 99  \w   -117.00 -68.00   0.50    0.05    --  -45.17 -57.00  60.00   98
100  \w    -97.00 -62.00   0.50    0.06    --  -84.00 -64.00-106.55   70
101  \w   -156.00 -78.00   0.50    0.06    -- -100.00 -64.00 -93.19  156
102  \w   -144.00 -85.00   0.50    0.06    -- -100.00-121.00 -38.00  118
103  \w   -137.00-112.00   0.50    0.06    -- -100.00-153.00 162.00   50
104  \w    -54.00 -27.00   0.50    0.06    -- -100.00  45.00 -90.00   54
105  \w    -53.00 -28.00   0.50    0.06    -- -100.00  61.00 -90.00   50
106  \w    -54.00 -25.00   0.50    0.06    -- -100.00  45.00  60.00   58
107  \w    -54.00 -25.00   0.50    0.06    -- -100.00  45.00  90.00   58
108  \w    -91.00 -24.00   0.50    0.05    --  -45.17 121.00  44.00  134
109  \w   -109.00 -52.00   0.50    0.06    -- -100.00 125.00   0.00  114
110  \w   -104.00 -72.00   0.50    0.05    --  -45.17 153.00-156.00   64
111  \w   -112.00 -49.00   0.50    0.06    -- -100.00 125.00-180.00  126
112  \w   -107.00 -82.00   0.50    0.06    -- -100.00 153.00-156.00   50
113  \w    -64.00 -38.00   0.50    0.06    -- -100.00 153.00-156.00   52
114  \w   -109.00 -68.00   0.50    0.06    -- -100.00 121.00  44.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0323082000
_diffrn_orient_matrix_UB_12      0.0268635000
_diffrn_orient_matrix_UB_13      -0.1127375000
_diffrn_orient_matrix_UB_21      0.1917907000
_diffrn_orient_matrix_UB_22      0.0286326000
_diffrn_orient_matrix_UB_23      -0.0055889000
_diffrn_orient_matrix_UB_31      0.0460201000
_diffrn_orient_matrix_UB_32      -0.1685297000
_diffrn_orient_matrix_UB_33      0.0123885000
_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  0.0480
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            27247
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.273
_diffrn_reflns_theta_min         3.258
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.580
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88246
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_description       block
_exptl_crystal_F_000             372
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3875
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0733
_refine_ls_R_factor_gt           0.0679
_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^)+(0.0720P)^2^+1.1078P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1848
_refine_ls_wR_factor_ref         0.1881
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3406
_reflns_number_total             3875
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00667h2.cif
_cod_data_source_block           yuanmeng-dchsh_0706-1_auto
_cod_depositor_comments
'Adding full bibliography for 7160604--7160605.cif.'
_cod_database_code               7160604
_shelx_shelxl_version_number     2018/3
_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:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C11(H11A,H11B), C16(H16A,H16B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C13(H13), C14(H14), C18(H18), C21(H21)
2.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              17708
_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 1.282
_oxdiff_exptl_absorpt_empirical_full_min 0.576