Chiral 4-Aryl-pyridine-N-oxide Nucleophilic Catalysts: Design, Synthesis, and Application in Acylative Dynamic Kinetic Resolution
Xie, Ming-Sheng; Shan, Meng; Li, Ning; Chen, Yang-Guang; Wang, Xiao-Bing; Cheng, Xuan; Tian, Yin; Wu, Xiao-Xia; Deng, Yun; Qu, Gui-Rong; Guo, Hai-Ming; ACS Catalysis  (2021) 877–891; doi:10.1021/acscatal.1c04923

data_4519238
_publ_section_title
;
 Chiral 4-Aryl-pyridine-N-oxide Nucleophilic Catalysts: Design, Synthesis,
 and Application in Acylative Dynamic Kinetic Resolution
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              877
_journal_page_last               891
_journal_paper_doi               10.1021/acscatal.1c04923
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H17 Br N4 O2'
_chemical_formula_sum            'C14 H17 Br N4 O2'
_chemical_formula_weight         353.23
_chemical_name_systematic        4p
_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     iterative
_audit_creation_date             2021-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.252(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1856(4)
_cell_length_b                   6.3673(2)
_cell_length_c                   21.5285(7)
_cell_measurement_reflns_used    9926
_cell_measurement_temperature    149.99
_cell_measurement_theta_max      78.32
_cell_measurement_theta_min      3.84
_cell_volume                     1625.90(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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_temperature      149.99
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0733
_diffrn_reflns_av_unetI/netI     0.0572
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            30626
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.112
_diffrn_reflns_theta_min         3.726
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.535
_exptl_absorpt_correction_T_max  0.7542
_exptl_absorpt_correction_T_min  0.3799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1588 before and 0.1089 after correction. The Ratio of minimum to maximum transmission is 0.5037. The \l/2 correction factor is Not present.'
_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    1.443
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.608
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Flack x determined using 2450 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.109(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         6341
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0558P)^2^+0.6371P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.818
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5859
_reflns_number_total             6341
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04923_si_003.cif
_cod_data_source_block           cu_0121_2_0m
_cod_database_code               4519238
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.619
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C6(H6), C20(H20)
3.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C3(H3), C2(H2), C14(H14), C27(H27), C17(H17), C16(H16), C28(H28)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C26(H26A,H26B,H26C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              55632
_shelx_hkl_checksum              1303
_olex2_submission_special_instructions 'No special instructions were received'