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_7249741
_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         'C24 H19 Br F3 N O2, C4 H8 O'
_chemical_formula_sum            'C28 H27 Br F3 N O3'
_chemical_formula_weight         562.41
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-13
_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                   5.8722(4)
_cell_length_b                   15.5610(10)
_cell_length_c                   28.0723(18)
_cell_measurement_reflns_used    7113
_cell_measurement_temperature    170
_cell_measurement_theta_max      63.185
_cell_measurement_theta_min      3.148
_cell_volume                     2565.2(3)
_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 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0736
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            15090
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        63.595
_diffrn_reflns_theta_max         63.595
_diffrn_reflns_theta_min         3.148
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.637
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.5659
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1292 before and 0.0815 after correction.
The Ratio of minimum to maximum transmission is 0.7521.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_description       needle
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 1156 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         4137
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0324P)^2^+0.0224P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0806
_refine_ls_wR_factor_ref         0.0883
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3448
_reflns_number_total             4137
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc05739b2.cif
_cod_data_source_block           202418424_0m
_cod_depositor_comments
'Adding full bibliography for 7249740--7249741.cif.'
_cod_database_code               7249741
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.760
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C14(H14), C12(H12), C2(H2A), C6(H6), C3(H3), C16(H16), C15(H15),
 C13(H13), C18(H18), C5(H5), C8(H8), C20(H20), C24(H24), C21(H21), C22(H22),
 C23(H23)
2.d Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'