Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation
Bhunia, Mrinal; Sahoo, Sumeet Ranjan; Das, Arpan; Ahmed, Jasimuddin; P., Sreejyothi; Mandal, Swadhin K.; Chemical Science 11 (2020) 1848–1854; doi:10.1039/C9SC05953A

data_1556844
_publ_section_title
;
 Transition metal-free catalytic reduction of primary amides using an
 abnormal NHC based potassium complex: integrating nucleophilicity with
 Lewis acidic activation
;
_journal_issue                   7
_journal_name_full               'Chemical Science'
_journal_page_first              1848
_journal_page_last               1854
_journal_paper_doi               10.1039/C9SC05953A
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C45 H57 B N2 O2'
_chemical_formula_sum            'C45 H57 B N2 O2'
_chemical_formula_weight         668.73
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-02 deposited with the CCDC.	2019-12-27 downloaded from the CCDC.
;
_cell_angle_alpha                85.238(4)
_cell_angle_beta                 75.946(4)
_cell_angle_gamma                75.838(5)
_cell_formula_units_Z            2
_cell_length_a                   9.6381(5)
_cell_length_b                   11.4850(6)
_cell_length_c                   19.0369(9)
_cell_measurement_reflns_used    6522
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      65.6220
_cell_measurement_theta_min      2.3800
_cell_volume                     1981.44(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9580
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -51.00   64.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472  -57.0000 -180.0000 115

  2 omega  -13.00  102.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472   57.0000  120.0000 115

  3 omega  -13.00  102.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472   57.0000 -180.0000 115

  4 omega  -13.00  102.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472   57.0000   60.0000 115

  5 omega   57.00  123.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472  178.0000  150.0000 66

  6 omega  -13.00  102.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       25.6472   57.0000    0.0000 115

  7 omega  100.00  153.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  111.0000  -30.0000 53

  8 omega   57.00  150.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  178.0000   60.0000 93

  9 omega  100.00  153.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  111.0000   60.0000 53

 10 omega   57.00  150.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  178.0000  150.0000 93

 11 omega  -13.00  152.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236   30.0000 -120.0000 165

 12 omega  100.00  153.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  111.0000  -60.0000 53

 13 omega   27.00  145.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236   61.0000   30.0000 118

 14 omega   22.00  154.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236   77.0000   90.0000 132

 15 omega  100.00  153.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  111.0000    0.0000 53

 16 omega   57.00  150.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236  178.0000 -120.0000 93

 17 omega    0.00  138.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       66.8236   30.0000    0.0000 138

 18 omega  123.00  149.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000  120.0000 26

 19 omega   22.00   48.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000  120.0000 26

 20 omega  122.00  148.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   54.0000  -60.0000 26

 21 omega  134.00  165.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   54.0000 -150.0000 31

 22 omega   84.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   54.0000  -60.0000 27

 23 omega   85.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -65.0000  -90.0000 26

 24 omega  135.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  138.0000   90.0000 42

 25 omega   77.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000 -180.0000 31

 26 omega   58.00   84.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000  120.0000 26

 27 omega   75.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000    0.0000 26

 28 omega   34.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000   30.0000 67

 29 omega   35.00   65.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000    0.0000 30

 30 omega  127.00  153.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  138.0000 -180.0000 26

 31 omega   81.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000    0.0000 97

 32 omega  106.00  145.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000  120.0000 39

 33 omega   87.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  138.0000 -180.0000 25

 34 omega   54.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000  120.0000 36

 35 omega   66.00  105.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 39

 36 omega  102.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  104.0000  -60.0000 76

 37 omega   66.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000 -150.0000 47

 38 omega  148.00  175.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   43.0000 -180.0000 27

 39 omega  112.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 66

 40 omega   22.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -150.0000 90

 41 omega  116.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -150.0000 31

 42 omega   35.00   61.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000    0.0000 26

 43 omega  109.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  104.0000  -90.0000 68

 44 omega  129.00  156.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   42.1347 27

 45 omega   66.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   42.1347 44

 46 omega  140.00  167.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  138.0000   60.0000 27

 47 omega   23.00   58.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000  150.0000 35

 48 omega   75.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000  -90.0000 102

 49 omega  117.00  164.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  104.0000   60.0000 47

 50 omega  152.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  138.0000  -60.0000 26

 51 omega   89.00  128.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   43.0000 -180.0000 39

 52 omega   82.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 31

 53 omega   74.00  121.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -129.0000  139.8282 47

 54 omega  106.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000 -120.0000 41

 55 omega   29.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -65.0000   60.0000 80

 56 omega   28.00   57.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -129.0000  139.8282 29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0977046000
_diffrn_orient_matrix_UB_12      -0.0215838000
_diffrn_orient_matrix_UB_13      0.0746449000
_diffrn_orient_matrix_UB_21      -0.0471273000
_diffrn_orient_matrix_UB_22      -0.0992453000
_diffrn_orient_matrix_UB_23      -0.0317958000
_diffrn_orient_matrix_UB_31      0.1301178000
_diffrn_orient_matrix_UB_32      -0.0939954000
_diffrn_orient_matrix_UB_33      0.0195134000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0436
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16871
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        65.913
_diffrn_reflns_theta_max         65.913
_diffrn_reflns_theta_min         2.393
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.513
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52439
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
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
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_exptl_crystal_density_diffrn    1.121
_exptl_crystal_F_000             724
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         6844
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0484
_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^)+(0.0641P)^2^+0.2445P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1208
_refine_ls_wR_factor_ref         0.1314
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5448
_reflns_number_total             6844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05953a2.cif
_cod_data_source_block           mbcbad
_cod_depositor_comments
;Adding full bibliography for 1556844.cif.

 Adding full bibliography for 1556844.cif.
;
_cod_database_code               1556844
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O B'
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.904
_reflns_odcompleteness_completeness 96.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C19(H19), C29(H29), C37(H37), B1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C16(H16), C17(H17), C18(H18),
 C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C33(H33), C34(H34), C35(H35)
2.c Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c), C12(H12a,H12b,H12c), C20(H20a,H20b,H20c), C21(H21a,H21b,
 H21c), C28(H28a,H28b,H28c), C30(H30a,H30b,H30c), C38(H38b,H38a,H38c), C39(H39a,
 H39b,H39c), C42(H42a,H42b,H42c), C43(H43a,H43b,H43c), C45(H45a,H45b,H45c),
 C46(H46a,H46b,H46c)
;
_shelx_res_checksum              58278
_olex2_date_sample_data_collection 2019-02-07
_olex2_submission_special_instructions 'No special instructions were received'