Cu-catalyzed [1,3]-asymmetric methoxy rearrangement of N-methoxyanilines: mechanistic insight
Masukawa, Kazuki; Kojima, Amu; Sato, Takuma; Terada, Masahiro; Nakamura, Itaru; Catalysis Science & Technology 15 (2025) 2138–2142; doi:10.1039/D5CY00106D

data_1573983
_publ_section_title
;
 Cu-catalyzed [1,3]-asymmetric methoxy rearrangement of N-methoxyanilines:
 mechanistic insight
;
_journal_issue                   7
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2138
_journal_page_last               2142
_journal_paper_doi               10.1039/D5CY00106D
_journal_volume                  15
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H24 Br N O2'
_chemical_formula_sum            'C20 H24 Br N O2'
_chemical_formula_weight         390.31
_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     dual
_audit_creation_date             2023-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-01-08 deposited with the CCDC.	2025-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.033(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4950(6)
_cell_length_b                   15.3001(10)
_cell_length_c                   11.7177(8)
_cell_measurement_reflns_used    4856
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.672
_cell_measurement_theta_min      2.365
_cell_volume                     1867.4(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker D8 Venture'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            'PHOTON III'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'multilayered conforcal mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1202
_diffrn_reflns_av_unetI/netI     0.0836
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            59545
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.520
_diffrn_reflns_theta_min         1.955
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.213
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1062 before and 0.0901 after correction.
The Ratio of minimum to maximum transmission is 0.8262.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.828
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2534 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.038(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         8582
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0477
_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^)+(0.0385P)^2^+0.9583P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0966
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                6814
_reflns_number_total             8582
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00106d2.cif
_cod_data_source_block           C20H24Br1N1O2_P21
_cod_depositor_comments
;
          Adding full bibliography for 1573983.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C40 H48 Br2 N2 O4'
_cod_original_formula_weight         780.62
_cod_original_formula_moiety         '2(C20 H24 Br N O2)'
_cod_original_formula_units_Z            2
_cod_database_code               1573983
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.809
_shelx_estimated_absorpt_t_min   0.666
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C8(H8), C12(H12), C13(H13), C15(H15), C22(H22), C23(H23),
 C28(H28), C34(H34), C39(H39), C40(H40)
2.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C)
;
_olex2_exptl_crystal_mounting_method loop
_olex2_submission_special_instructions 'No special instructions were received'