Direct asymmetric α-C–H functionalization of N-unprotected allylamine catalyzed by chiral pyridoxal
Liang, Hanyu; Cao, Jiaxuan; Zhang, Hailong; Huang, Longjie; Liu, Siqi; Wu, Tianhao; Xiao, Xiao; Zhao, Baoguo; Green Chemistry 27 (2025) 1374–1380; doi:10.1039/D4GC05739B

data_7249740
_publ_section_title
;
 Direct asymmetric \a-C--H functionalization of N-unprotected allylamine
 catalyzed by chiral pyridoxal
;
_journal_issue                   5
_journal_name_full               'Green Chemistry'
_journal_page_first              1374
_journal_page_last               1380
_journal_paper_doi               10.1039/D4GC05739B
_journal_volume                  27
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C15 H14 F3 N O2'
_chemical_formula_sum            'C15 H14 F3 N O2'
_chemical_formula_weight         297.27
_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     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2l9dkw
_audit_creation_date             2024-10-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-19 deposited with the CCDC.	2025-01-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.8059(3)
_cell_length_b                   9.5499(4)
_cell_length_c                   22.0878(10)
_cell_measurement_reflns_used    9852
_cell_measurement_temperature    170
_cell_measurement_theta_max      74.406
_cell_measurement_theta_min      5.045
_cell_volume                     1435.61(11)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker d8 venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0578
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            12166
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.688
_diffrn_reflns_theta_min         5.045
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.012
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.4627
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1771 before and 0.0795 after correction.
The Ratio of minimum to maximum transmission is 0.6138.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       block
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1052 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.12(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         2907
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0614P)^2^+0.1839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                2682
_reflns_number_total             2907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc05739b2.cif
_cod_data_source_block           cu_20241841_0m
_cod_depositor_comments
'Adding full bibliography for 7249740--7249741.cif.'
_cod_database_code               7249740
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.888
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C5(H5), C14(H14), C12(H12), C1(H1C), C13(H13), C4(H4), C3(H3),
  C6(H6)
2.c Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_olex2_submission_special_instructions 'No special instructions were received'