Diastereodivergent Synthesis of Chiral α-Aminoketones via a Catalytic O–H Insertion/Barnes–Claisen Rearrangement Reaction
Liu, Yun; Chen, Yushuang; Yihuo, Aying; Zhou, Yuqiao; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming; ACS Catalysis  (2022) 1784–1790; doi:10.1021/acscatal.1c05789

data_4519291
_publ_section_title
;
 Diastereodivergent Synthesis of Chiral \a-Aminoketones via a Catalytic
 O--H Insertion/Barnes--Claisen Rearrangement Reaction
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1784
_journal_page_last               1790
_journal_paper_doi               10.1021/acscatal.1c05789
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H21 N O4 S'
_chemical_formula_sum            'C20 H21 N O4 S'
_chemical_formula_weight         371.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 94.297(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.954(3)
_cell_length_b                   8.0412(11)
_cell_length_c                   10.4938(14)
_cell_measurement_reflns_used    9785
_cell_measurement_temperature    172(2)
_cell_measurement_theta_max      68.29
_cell_measurement_theta_min      4.22
_cell_volume                     1931.5(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick 2008)'
_diffrn_ambient_temperature      172(2)
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker D8 Venture Photon II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20837
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.435
_diffrn_reflns_theta_min         3.862
_exptl_absorpt_coefficient_mu    1.692
_exptl_absorpt_correction_T_max  0.8508
_exptl_absorpt_correction_T_min  0.6529
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'SADABS (Krause et al., 2015)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.154
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.248
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
; 
 Flack x determined using 1471 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.085(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         3388
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0298
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0437P)^2^+0.7411P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0805
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                3337
_reflns_number_total             3388
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05789_si_002.cif
_cod_data_source_block           liy012
_cod_original_cell_volume        1931.5(5)
_cod_original_sg_symbol_H-M      'C 2'
_cod_database_code               4519291
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.612
_shelx_estimated_absorpt_t_max   0.781
_shelx_res_checksum              64453
_shelx_hkl_checksum              80390