Kinetic Resolution of α-Tertiary Propargylic Amines through Asymmetric Remote Aminations of Anilines
Pan, Yongkai; Wang, Donglei; Chen, Yunrong; Zhang, DeKun; Liu, Wei; Yang, Xiaoyu; ACS Catalysis  (2021) 8443–8448; doi:10.1021/acscatal.1c02331

data_4518853
_publ_section_title
;
 Kinetic Resolution of \a-Tertiary Propargylic Amines through Asymmetric
 Remote Aminations of Anilines
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              8443
_journal_page_last               8448
_journal_paper_doi               10.1021/acscatal.1c02331
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H15 N'
_chemical_formula_sum            'C16 H15 N'
_chemical_formula_weight         221.29
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-09
_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                   9.9852(3)
_cell_length_b                   9.9852(3)
_cell_length_c                   12.7680(4)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.92
_cell_measurement_theta_min      4.43
_cell_volume                     1273.02(7)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.997
_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  0.0773
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            40590
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.458
_diffrn_reflns_theta_min         4.428
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.509
_exptl_absorpt_correction_T_max  0.7542
_exptl_absorpt_correction_T_min  0.6506
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1385 before and 0.0857 after correction.
The Ratio of minimum to maximum transmission is 0.8626.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1126 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2744
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0396P)^2^+0.3775P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.904
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                2540
_reflns_number_total             2744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c02331_si_002.cif
_cod_data_source_block           cu_pyk_s_3_0m
_cod_original_cell_volume        1273.02(9)
_cod_database_code               4518853
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.905
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N001(H001), C004(H004), C006(H006), C009(H009), C00A(H00A), C00C(H00E),
 C00D(H00F), C00E(H00G), C00F(H00H), C00G(H00I), C00H(H00J)
2.b Idealised Me refined as rotating group:
 C00B(H00B,H00C,H00D)
2.c :
 C005(H005)
;
_shelx_res_checksum              42356
_shelx_hkl_checksum              89212
_olex2_submission_special_instructions 'No special instructions were received'