Cobalt-Catalyzed Direct α-Hydroxymethylation of Amides with Methanol as a C1 Source
Ma, Ben; Sun, Rong-Xia; Yang, Jingya; Chemical Communications  (2022) –; doi:10.1039/D1CC06501G

data_7129463
_publ_section_title
;
 Cobalt-Catalyzed Direct \a-Hydroxymethylation of Amides with Methanol as
 a C1 Source
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06501G
_journal_year                    2022
_chemical_formula_moiety         'C16 H16 F N O2'
_chemical_formula_sum            'C16 H16 F N O2'
_chemical_formula_weight         273.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-29
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-09-14 deposited with the CCDC.	2021-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.5402(18)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.0338(3)
_cell_length_b                   11.15970(19)
_cell_length_c                   14.0652(3)
_cell_measurement_reflns_used    7217
_cell_measurement_temperature    302.01(10)
_cell_measurement_theta_max      75.5930
_cell_measurement_theta_min      3.1150
_cell_volume                     2806.17(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      302.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.959
_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     35.00  68.00   0.50    0.24    --  103.99 -61.00-150.00   66
  2  \w     31.00  62.00   0.50    0.24    --  103.99 -61.00 -90.00   62
  3  \w     41.00  67.00   0.50    0.24    --  103.99 -77.00 -60.00   52
  4  \w     33.00  73.00   0.50    0.24    --  103.99 -61.00 -30.00   80
  5  \w    153.00 178.00   0.50    0.24    --  103.99  34.00  56.00   50
  6  \w     35.00 115.00   0.50    0.06    --   46.20  34.00  56.00  160
  7  \w     16.00  41.00   0.50    0.06    --   46.20 -34.00-100.00   50
  8  \w    -32.00  17.00   0.50    0.06    --  -46.20  34.00  56.00   98
  9  \w    -68.00 -29.00   0.50    0.24    -- -102.00  61.00 120.00   78
 10  \w    -69.00 -38.00   0.50    0.24    -- -102.00  61.00  30.00   62
 11  \w    -69.00 -34.00   0.50    0.24    -- -102.00  61.00  60.00   70
 12  \w    -98.00 -30.00   0.50    0.24    -- -102.00  77.00 -30.00  136
 13  \w    -65.00 -29.00   0.50    0.24    -- -102.00  61.00 150.00   72
 14  \w    -62.00 -32.00   0.50    0.24    -- -102.00  61.00-120.00   60
 15  \w    -62.00 -33.00   0.50    0.24    -- -102.00  61.00-150.00   58
 16  \w    -69.00 -29.00   0.50    0.24    -- -102.00  61.00-180.00   80
 17  \w    -40.00  25.00   0.50    0.06    --  -46.20  37.00-150.00  130
 18  \w   -175.00 -89.00   0.50    0.24    -- -102.00 -34.00-100.00  172
 19  \w   -122.00 -95.00   0.50    0.24    -- -102.00-125.00  60.00   54
 20  \w   -175.00-146.00   0.50    0.24    -- -102.00-125.00  60.00   58
 21  \w   -110.00 -34.00   0.50    0.06    --  -46.20 -34.00-100.00  152
 22  \w     72.00 106.00   0.50    0.24    --  103.99-125.00-120.00   68
 23  \w     66.00 103.00   0.50    0.24    --  103.99 -94.00 -60.00   74
 24  \w     35.00  65.00   0.50    0.24    --  103.99-125.00-120.00   60
 25  \w     39.00  67.00   0.50    0.24    --  103.99 -94.00-180.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0786042000
_diffrn_orient_matrix_UB_12      -0.0560260000
_diffrn_orient_matrix_UB_13      -0.0191966000
_diffrn_orient_matrix_UB_21      -0.0113970000
_diffrn_orient_matrix_UB_22      0.0229564000
_diffrn_orient_matrix_UB_23      0.1051213000
_diffrn_orient_matrix_UB_31      -0.0333901000
_diffrn_orient_matrix_UB_32      0.1240707000
_diffrn_orient_matrix_UB_33      -0.0280932000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9716
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.694
_diffrn_reflns_theta_min         4.671
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.778
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87509
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       block
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.0034(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2801
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0649P)^2^+0.8910P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1168
_refine_ls_wR_factor_ref         0.1195
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2552
_reflns_number_total             2801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06501g2.cif
_cod_data_source_block           sunrongxia_0428-1_auto
_cod_original_cell_volume        2806.18(9)
_cod_database_code               7129463
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              20085
_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 1.955
_oxdiff_exptl_absorpt_empirical_full_min 0.375