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_4135324
_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 unk
_chemical_formula_moiety         'C26 H37 N4 O2, C26 H36 N4 O2, Cl, 2(H2 O)'
_chemical_formula_sum            'C52 H77 Cl N8 O6'
_chemical_formula_weight         945.66
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-07-25
_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                   16.2461(2)
_cell_length_b                   16.4020(2)
_cell_length_c                   19.8014(2)
_cell_measurement_reflns_used    32344
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      72.4380
_cell_measurement_theta_min      3.8800
_cell_volume                     5276.45(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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   -114.00 -20.00   1.00    1.00    --  -40.64 158.00 148.00   94
  2  \w     29.00 114.00   1.00    1.62    --  103.55-119.00 -90.00   85
  3  \w     68.00 178.00   1.00    1.62    --  103.55  23.00 -80.00  110
  4  \w    101.00 178.00   1.00    1.62    --  103.55 104.00  94.00   77
  5  \w   -117.00 -51.00   1.00    1.00    --  -40.64-158.00 115.00   66
  6  \w    -92.00  -2.00   1.00    1.00    --  -40.64 125.00-120.00   90
  7  \w   -115.00 -16.00   1.00    1.00    --  -40.64 -38.00 -90.00   99
  8  \w     27.00 112.00   1.00    1.62    --  103.55-111.00  90.00   85
  9  \w     27.00 112.00   1.00    1.62    --  103.55-111.00  30.00   85
 10  \w     31.00 133.00   1.00    1.62    --  103.55 -61.00 120.00  102
 11  \w     31.00 129.00   1.00    1.62    --  103.55 -45.00-120.00   98
 12  \w    -65.00  34.00   1.00    1.00    --  -40.64  38.00  90.00   99
 13  \w   -113.00 -12.00   1.00    1.00    --  -40.64 -57.00  30.00  101
 14  \w   -113.00 -12.00   1.00    1.00    --  -40.64 -57.00 150.00  101
 15  \w     78.00 177.00   1.00    1.62    --  103.55  45.00 120.00   99
 16  \w     78.00 177.00   1.00    1.62    --  103.55  45.00-180.00   99
 17  \w     71.00 178.00   1.00    1.62    --  103.55  77.00 -60.00  107
 18  \w     74.00 176.00   1.00    1.62    --  103.55  61.00  60.00  102
 19  \w     71.00 178.00   1.00    1.62    --  103.55  77.00-120.00  107
 20  \w     51.00 178.00   1.00    1.62    --  103.55  15.00  60.00  127
 21  \w   -117.00  -8.00   1.00    1.00    --  -40.64 -77.00 -90.00  109
 22  \w   -117.00  -8.00   1.00    1.00    --  -40.64 -77.00 120.00  109
 23  \w      1.00  82.00   1.00    1.00    --   40.64 -99.00 150.00   81
 24  \w     71.00 178.00   1.00    1.62    --  103.55  77.00 120.00  107
 25  \w     71.00 171.00   1.00    1.62    --  103.55  77.00   0.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0276943000
_diffrn_orient_matrix_UB_12      0.0622903000
_diffrn_orient_matrix_UB_13      -0.0536221000
_diffrn_orient_matrix_UB_21      -0.0087926000
_diffrn_orient_matrix_UB_22      -0.0691725000
_diffrn_orient_matrix_UB_23      -0.0521317000
_diffrn_orient_matrix_UB_31      -0.0902492000
_diffrn_orient_matrix_UB_32      -0.0124364000
_diffrn_orient_matrix_UB_33      0.0215267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0797
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            73415
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.249
_diffrn_reflns_theta_min         3.499
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.074
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (Rigaku Oxford Diffraction, 2019)
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    1.190
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3707 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     640
_refine_ls_number_reflns         10382
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0760P)^2^+0.9198P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1235
_refine_ls_wR_factor_ref         0.1305
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                9138
_reflns_number_total             10382
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09075_si_004.cif
_cod_data_source_block           hb-20190527
_cod_database_code               4135324
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.882
_diffrn_oxdiff_digest_frames
;
01fb2a87fa8a9de8bc09106c2bccf3ef6f0003329af
;
_diffrn_oxdiff_digest_hkl
;
01a885fa7fd34894e6b839533ca97c73320ab4
;
_reflns_odcompleteness_completeness 99.94
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 C28-C29 \\sim C28-C29A
 with sigma of 0.02
 C28-C1AA \\sim C28-C1AB
 with sigma of 0.02
3. Others
 Sof(H28a)=Sof(C29A)=Sof(H29d)=Sof(H29e)=Sof(H29f)=Sof(C1AB)=Sof(H1Ad)=
 Sof(H1Ae)=Sof(H1Af)=1-FVAR(1)
 Sof(H28)=Sof(C29)=Sof(H29a)=Sof(H29b)=Sof(H29c)=Sof(C1AA)=Sof(H1Aa)=Sof(H1Ab)=
 Sof(H1Ac)=FVAR(1)
4.a Free rotating group:
 O0AA(H0Ad,H0Ae), O1AA(H1Ag,H1Ah)
4.b Ternary CH refined with riding coordinates:
 C39(H39), C9(H9), C58(H58), C61(H61), C30(H30), C28(H28), C28(H28a)
4.c Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C42(H42a,H42b), C41(H41a,H41b), C10(H10a,H10b), C11(H11a,
 H11b), C40(H40a,H40b), C20(H20a,H20b), C50(H50a,H50b), C47(H47a,H47b),
 C17(H17a,H17b), C18(H18a,H18b), C49(H49a,H49b), C19(H19a,H19b), C48(H48a,H48b)
4.d Aromatic/amide H refined with riding coordinates:
 N15(H15), N45(H45), C2(H2), C37(H37), C5(H5), C34(H34), C35(H35), C6(H6),
 C26(H26), C24(H24), C56(H56), C25(H25), C54(H54), C55(H55)
4.e Idealised Me refined as rotating group:
 C63(H63a,H63b,H63c), C62(H62a,H62b,H62c), C60(H60a,H60b,H60c), C59(H59a,H59b,
 H59c), C31(H31a,H31b,H31c), C29(H29a,H29b,H29c), C0AA(H0Aa,H0Ab,H0Ac),
 C1AA(H1Aa,H1Ab,H1Ac), C29A(H29d,H29e,H29f), C1AB(H1Ad,H1Ae,H1Af)
4.f Idealised tetrahedral OH refined as rotating group:
 O21(H21)
;
_shelx_res_checksum              63025
_shelx_hkl_checksum              87089
_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 5.124
_oxdiff_exptl_absorpt_empirical_full_min 0.511