Electrochemical regioselective reduction of α-keto amides with methanol as a hydrogen source.
Zhang, Jin-Jin; Wang, Jing-Hong; Sang, Ya-Hui; Qin, Hai-Juan; Chen, Chao; Liu, Wei; Organic & biomolecular chemistry 23 (2025) 4922–4926; doi:10.1039/d5ob00384a

data_7160507
_publ_section_title
;
 Electrochemical regioselective reduction of &#x3b1;-keto amides with
 methanol as a hydrogen source.
;
_journal_issue                   20
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4922
_journal_page_last               4926
_journal_paper_doi               10.1039/d5ob00384a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C27 H23 N O2, C H4 O'
_chemical_formula_sum            'C28 H27 N O3'
_chemical_formula_weight         425.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-04 deposited with the CCDC.	2025-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.9085(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.36186(16)
_cell_length_b                   16.38187(20)
_cell_length_c                   15.3770(3)
_cell_measurement_reflns_used    21238
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.7720
_cell_measurement_theta_min      3.9590
_cell_volume                     2298.69(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -101.00 -62.00   0.50    0.05    --  -62.90 -15.00 120.00   78
  2  \w    -64.00 -27.00   0.50    0.05    --  -62.90 125.00-120.00   74
  3  \w   -100.00 -66.00   0.50    0.05    --  -62.90 -15.00-150.00   68
  4  \w   -104.00 -54.00   0.50    0.05    --  -62.90 -15.00-180.00  100
  5  \w     45.00  95.00   0.50    0.05    --   76.05-125.00 150.00  100
  6  \w     44.00  91.00   0.50    0.05    --   76.05-125.00 -90.00   94
  7  \w   -121.00 -96.00   0.50    0.05    --  -76.93 -15.00 120.00   50
  8  \w   -116.00 -87.00   0.50    0.05    --  -76.93 -15.00-120.00   58
  9  \w    -97.00 -50.00   0.50    0.05    --  -77.75 125.00 120.00   94
 10  \w   -119.00 -90.00   0.50    0.05    --  -77.75 -15.00-180.00   58
 11  \w   -109.00 -83.00   0.50    0.05    --  -77.75 -15.00 -90.00   52
 12  \w   -121.00 -91.00   0.50    0.05    --  -77.75 -15.00 -30.00   60
 13  \w   -127.00-101.00   0.50    0.05    --  -82.00 -40.00-123.79   52
 14  \w   -127.00-102.00   0.50    0.05    --  -82.00 -39.00 -65.72   50
 15  \w   -127.00-102.00   0.50    0.05    --  -82.00 -40.00 -30.44   50
 16  \w   -127.00-102.00   0.50    0.05    --  -82.00 -38.00-161.43   50
 17  \w    -96.00 -59.00   0.50    0.05    --  -82.00 116.00  91.84   74
 18  \w   -127.00-102.00   0.50    0.05    --  -82.00 -39.00 102.38   50
 19  \w    -74.00 -41.00   0.50    0.05    --  -82.00 137.00 130.69   66
 20  \w   -100.00 -75.00   0.50    0.05    --  -82.00 125.00  59.52   50
 21  \w    -82.00 -56.00   0.50    0.05    --  -82.00 124.00-158.55   52
 22  \w    -92.00 -67.00   0.50    0.05    --  -82.00 112.00  56.41   50
 23  \w    -69.00 -44.00   0.50    0.05    --  -82.00 125.00  59.52   50
 24  \w   -101.00 -74.00   0.50    0.05    --  -82.00 126.00  -5.28   54
 25  \w    -69.00 -41.00   0.50    0.05    --  -82.00 126.00  -5.28   56
 26  \w   -101.00 -75.00   0.50    0.05    --  -82.00 134.00 -63.85   52
 27  \w    -72.00 -41.00   0.50    0.05    --  -82.00 134.00 -63.85   62
 28  \w    -78.00 -43.00   0.50    0.05    --  -82.00 109.00  48.64   70
 29  \w    -74.00 -43.00   0.50    0.05    --  -82.00 134.00-162.96   62
 30  \w    -79.00 -43.00   0.50    0.05    --  -82.00 137.00-143.37   72
 31  \w   -127.00-102.00   0.50    0.05    --  -82.00 -38.00 173.52   50
 32  \w    -95.00 -70.00   0.50    0.05    --  -82.00 114.00  46.71   50
 33  \w    -74.00 -41.00   0.50    0.05    --  -82.00 134.00  33.32   66
 34  \w    -67.00 -41.00   0.50    0.05    --  -82.00 129.00 -97.17   52
 35  \w    -71.00 -46.00   0.50    0.05    --  -82.00  99.00  91.12   50
 36  \w    -96.00 -44.00   0.50    0.05    --  -82.00 116.00  60.96  104
 37  \w   -127.00-102.00   0.50    0.05    --  -82.00 -38.00 133.59   50
 38  \w    -67.00 -42.00   0.50    0.05    --  -82.00 135.00 156.35   50
 39  \w    -68.00 -43.00   0.50    0.05    --  -82.00 115.00-162.62   50
 40  \w    -79.00 -44.00   0.50    0.05    --  -82.00 138.00 120.46   70
 41  \w    -99.00 -55.00   0.50    0.05    --  -82.00 122.00 103.94   88
 42  \w    -92.00 -67.00   0.50    0.05    --  -82.00 112.00  31.67   50
 43  \w    -83.00 -58.00   0.50    0.05    --  -82.00 113.00-164.38   50
 44  \w    -67.00 -42.00   0.50    0.05    --  -82.00 140.00 -32.70   50
 45  \w    -99.00 -41.00   0.50    0.05    --  -82.00 125.00 -26.64  116
 46  \w    -69.00 -41.00   0.50    0.05    --  -82.00 124.00 -95.08   56
 47  \w   -108.00 -82.00   0.50    0.05    --  -82.00 140.00 -32.70   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0854542000
_diffrn_orient_matrix_UB_12      0.0028389000
_diffrn_orient_matrix_UB_13      -0.0980226000
_diffrn_orient_matrix_UB_21      0.1447213000
_diffrn_orient_matrix_UB_22      -0.0083891000
_diffrn_orient_matrix_UB_23      -0.0310943000
_diffrn_orient_matrix_UB_31      -0.0155718000
_diffrn_orient_matrix_UB_32      -0.0935956000
_diffrn_orient_matrix_UB_33      -0.0001190000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0256
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            28844
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.987
_diffrn_reflns_theta_min         3.998
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.630
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.265
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0042(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4712
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0454P)^2^+1.1075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4494
_reflns_number_total             4712
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00384a3.cif
_cod_data_source_block           exp_374_auto
_cod_depositor_comments          'Adding full bibliography for 7160507.cif.'
_cod_original_cell_volume        2298.69(6)
_cod_database_code               7160507
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H O N'
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.884
_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, All O(H) groups
2.a Riding coordinates:
 C10(H10)
2.b Aromatic/amide H refined with riding coordinates:
 N8(H8), C6(H6), C24(H24), C14(H14), C26(H26), C20(H20), C18(H18), C2(H2),
 C16(H16), C30(H30), C29(H29), C5(H5), C17(H17), C27(H27), C15(H15), C23(H23),
 C28(H28), C4(H4), C3(H3), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C)
2.d Idealised tetrahedral OH refined as rotating group:
 O11(H11), O31(H31)
;
_shelx_res_checksum              11223
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.604
_oxdiff_exptl_absorpt_empirical_full_min 0.339